狄、發明說明： 【發明所屬之技術領域】 本發明係關於一種石英晶體微天平之裝置，尤指一種 適用於監控環境中氣體成分之石英晶體微天平之裝置。 5 【先前技術】 石英晶體微天平（Quartz Crystal Microbalance，QCM)是一個 回靈敏度的量測儀器，其有效頻寬為2〜16 mHz，解析度為 〇_1 Hz，適用於微量物質的量測。石英晶體微天平由電子 10振盪電路、計頻器以及壓電石英晶體等三部分所構成。壓 電石英晶體是由石英晶片在其兩面各披覆一層金電極所構 成，為壓電感測晶片之訊號轉換元件，其可將感測分子所 檢測的結果轉換成電子訊號傳送。 金電極的作用主要是沿晶片泰面的垂直方向導入一振 15盪電場（〇sclllating electric field)，使晶片内部因反壓電效 應產生一機械振盪，若石英晶體的厚度一定，則此機械振 盪將以一固定的頻率產生，利用一適當的電子振盪電路， 即可將其共振頻率測定出來。依據Sauerbrey方程式，對 於AT-cut之石英壓電晶體，其電極表面質量的變化量 20與晶體振盈頻率變化量間會呈線性關係： AFocAm 故當壓電石英晶體吸附感測分子產生質量變化時，晶 振盪頻率會跟著變化，故可測知一氣體内之微量物質濃 1220687 石英晶體微天平在水份的量測方面，1997年美國 5616827號專利是以乾燥空氣的流量與水滲透管之滲透速率 調配水氣濃度，是一套動態量測系統。M. Neshkova等人在 1996 年 AnalyticaChimicaActa期刊第 332 期第 93-103 頁中發 5 表 ’’ Piezoelectric quartz crystal humidity sensor using chemically modified nitrated polystyrene as water sorbing coating”是以乾燥空氣與不同 飽和鹽液下產生的蒸氣，調配不同水氣含量做為量測標 準，同樣方法 Yongxiang Xu 等人在 2002 年 Progress in Organic Coatings 期刊第 45 期第 331-339 頁中發表之 “Water vapour in 10 the coatings of alkyd and polyurethane varnish”為恆溫下的水蒸氣做 為量測標準，而 Xi-Wen He 等人在 1996 年 Analytica Chimica Acta 期刊第 464 期第 57-64 頁中發表’’ Kinetic detection of benzene/chloroform and toluene/chloroform vapors using a single quartz piezoelectric crystal coated with calyx”是以苯/氯仿與曱苯/氯仿的 15 擴散管做量測標準，亦提到其具溫度控制系統，目的在於 使量測時的環境溫度維持在恆溫條件下303 K(30 °〇,此溫 度為氯仿脫附的最佳溫度點，但若要去除附著在感測晶片 上的測試物質仍需取出後再做處理。以上習知之裝置均屬 動態量測。而在Tatsuhiro Okada等人於2000年Analytica 20 Chimica期刊第421期第83-92頁中發表之”Simutaneous determination of the concentration of methanol and relative humidity based on a single Nafion (Ag)-coated quartz crystal microbalance”，是將定量 之曱醇與水注入定體積的測試槽中，量測QCM在不同濃 度的頻率變化量，屬於靜態量測的設計，其亦具溫度控制 25 系統，此溫度控制的目的在於使注入的液態樣品加快蒸發 7 速度，以縮短等待的時間。 綜上所述’在以石英晶體微天平做為微量水份的量測 儀器中，發現習知技藝之測試槽有幾項缺點：無同時具備 動靜態量測、無法在高溫量測、及沒有感測晶片再生的設 ^ 專’因此發明人引發改良測試槽的動機，亟思一種改 σ上述問4之「石英晶體微天平裝置」，幾經研究實驗終至 元成此項嘉惠世人之發明。 【發明内容】 ^本發明之主要目的係在提供一種石英晶體微天平之 表置俾此使石英晶片上之感測材料被測試物質填滿後， 毋須拆除量測裝置，即可將附著在晶片上的測試物質驅 並…5 了動、靜態量測的設計，可以調整測試環境的 溫度，屬於一套多功能的氣體測試裝置，可廣泛應用於監 控環境污染源上。 、 本發明之一種石英晶體微天平裝置，其係配合一樣品 二=量物質之量測，其包括一感測晶片·，用以吸附該 物質，而產生一機械振盪；一電子振盪電路，係與該 感測晶電性上相連，依該感測晶片所產生之該機械振 f，偵知該感測晶片因吸附該微量物質所造成之質量變化 二测試槽，用以容置該感測晶片，在量測時提供一定 辟m閉空間，至少一樣品入口，係位於該測試槽之一槽 壁^二用以將該樣品置入該測試槽；一樣品出口，係位於 、^槽之槽壁上，用以作為該樣品離開該測試槽之出 1220687 口； 一真空幫浦，係與該測試槽相通，以抽離附著於該感 測晶片之該微量物質；以及一溫度控制器，用以控制該測 試槽之溫度’作為高溫量測或該感測晶片再生時脫附該微 量物質之用。 【貫施方式】 本發明之石英晶體微天平裝置包括一感測晶片，其吸 附樣品内之微量物質，並可產生一機械振盪；一電子振盪 電路，較佳為以一穿通導引（feed thr〇ugh)與感測晶片電性 ίο上相連，其依感測晶片所產生之機械振盪變化，測定感測 晶片因吸附微量物質所造成之質量變化量；一測試槽，用 以容置感測晶片，在量測時提供一密閉空間；一位於測試 槽壁上之樣品入口，用以作為樣品進入測試槽之入口； 一 位於測试槽壁上之樣品出口，用以作為樣品離開測試槽之 15出口 ·，-溫度控制器，其控制測試槽之溫度，作為高溫量 測、液體樣品氣化、與感測材料再生使用；以及一與該測 试才曰相通之真空幫浦，以抽離附著於該感測.晶片之該微量 20 本發明之賴槽人π在關閉其絲意之出人口時為_ 注射口’可作樣品濃度之靜態量測。該注射口注入之樣』 通常為液態，並在注人後湘溫度控制器將液體氣化，^ =^口較佳為由-針頭、—針筒、與—橡皮塞所組成， 量之自動注射闕。本發明之裝置在樣品㈣ 心里/貝％ ’樣品出人口通常與氣體輸人與輸出管線和 9 連，較佳為包含一流量控制器與氣體輸入管線相連，用以 控2氣體樣品進入測試槽之流量；更佳為氣體輸入與輸出 之管線分別安裝一閥門以控制該氣體輸入與輸出管線之開 關。本發明之測試槽入口，其可為靜態量測之液體入口， 5亦可為動態量測之氣體入口，較佳為同時兼具動靜態量測 之入口，動靜態量測之樣品入口亦可為各自獨立之入口。 本發明之裝置中，感測晶片係由一石英晶片兩面各披 覆一層電極所構成，該電極可使石英晶片產生共振頻率， 其上並塗覆一感測材料，該感測材料可為一陶瓷材料、一 有機间为子材料或任何複合材料，以提供吸附該微量物質 之位置，5亥感測材料之選擇，係依據所需吸附之微量物質 不同而有所不同。而測試槽之材料並無限制，較佳由玻璃 或不銹鋼材質組成。在溫度控制方面，一溫度控制器通常 適時調整測試槽所需之溫度，如測試溫度、脫附溫度、盘 15液體樣品氣化溫度，並且在氣體輸入管線外圍較佳為以二 加熱帶包覆，以適時加熱氣體輸入管線内之樣品。 為能讓貴審查委員能更瞭解本發明之技術内容 舉三較佳具體實施例說明如下。在以下之三實施例中其均 使用同-裝置，故其同時具有動、靜態量測與再生功能， 20 其裝置如圖1所示。 實施例1 :動態量測 本發明之石英晶體微天平裂置，在本實施例中功 動態量測-氣體樣品内之微量物質（如水或甲笨等）。二 此裝置中，樣品藉由流量控制器9控制氣體輸入管線i内之 10 1220687 一固定濃度之標準源，並經由位於測D. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a device for quartz crystal microbalances, and more particularly to a device for quartz crystal microbalances suitable for monitoring the gas composition in the environment. 5 [Prior technology] Quartz Crystal Microbalance (QCM) is a sensitivity measurement instrument with an effective bandwidth of 2 ~ 16 mHz and a resolution of 0_1 Hz. It is suitable for the measurement of trace substances. . The quartz crystal microbalance is composed of three parts: an electronic 10 oscillation circuit, a frequency counter and a piezoelectric quartz crystal. Piezoelectric quartz crystals are composed of quartz wafers covered with a layer of gold electrodes on each side. They are signal conversion elements for piezoelectric inductive sensing wafers, which convert the results detected by the sensing molecules into electronic signals for transmission. The function of the gold electrode is to introduce a 15-oscillation electric field along the vertical direction of the wafer surface, so that a mechanical oscillation occurs in the wafer due to the anti-piezoelectric effect. If the thickness of the quartz crystal is constant, the mechanical oscillation It will be generated at a fixed frequency, and its resonance frequency can be measured by an appropriate electronic oscillation circuit. According to the Sauerbrey equation, for AT-cut quartz piezoelectric crystals, there is a linear relationship between the amount of change in the surface quality of the electrode 20 and the amount of crystal oscillation frequency change: AFocAm. The crystal oscillation frequency will change accordingly, so it can be known that the concentration of trace substances in a gas is 1220687. The quartz crystal microbalance is used for water measurement. It is a set of dynamic measurement system to adjust the water and gas concentration. M. Neshkova et al., In 1996, Analytica Chimica Acta Journal, 332, pages 93-103. Table 5 "Piezoelectric quartz crystal humidity sensor using chemically modified nitrated polystyrene as water sorbing coating" is produced under dry air and different saturated salt solutions. The same method was used in the "Water vapour in 10 the coatings of alkyd and polyurethane" published by Yongxiang Xu et al. In Progress in Organic Coatings, Issue 45, pages 331-339, 2002. "varnish" is the measurement standard for water vapor at constant temperature, and Xi-Wen He et al. published the "Kinetic detection of benzene / chloroform and toluene / chloroform" in Analytica Chimica Acta Journal, Issue 464, pages 57-64, 1996. Vapors using a single quartz piezoelectric crystal coated with calyx "is a measurement standard based on 15 diffusion tubes of benzene / chloroform and toluene / chloroform. It is also mentioned that it has a temperature control system to maintain the ambient temperature during measurement. 303 K (30 ° 〇 at constant temperature, this temperature is chloroform The optimum temperature point is attached, but if you want to remove the test substance attached to the sensor chip, you still need to take it out and deal with it. The conventional devices are dynamic measurement. In Tatsuhiro Okada et al., 2000 Analytica 20 Chimica, 2000 The issue of "Simutaneous determination of the concentration of methanol and relative humidity based on a single Nafion (Ag) -coated quartz crystal microbalance" was published in the issue 421, pages 83-92. In the test tank, the frequency change of QCM at different concentrations is measured. It is a static measurement design. It also has a temperature control system 25. The purpose of this temperature control is to accelerate the evaporation of the injected liquid sample 7 to reduce the waiting time. time. In summary, 'in the quartz crystal microbalance as a micro-moisture measuring instrument, I found that the test tank of the conventional technique has several disadvantages: no simultaneous dynamic and static measurement, no high temperature measurement, and no The design of the sensor chip regeneration is unique. Therefore, the inventor motivated the improvement of the test tank, and was thinking about a kind of "quartz crystal microbalance device" to change the above question. After several research experiments, this invention has benefited the world. . [Summary of the Invention] ^ The main purpose of the present invention is to provide a quartz crystal microbalance with a surface setting. After the sensing material on the quartz wafer is filled with the test substance, the measuring device can be attached to the wafer without removing the measuring device. The test substances on the drive are combined with ... 5 The design of dynamic and static measurement can adjust the temperature of the test environment. It belongs to a set of multifunctional gas test devices and can be widely used in monitoring environmental pollution sources. A quartz crystal microbalance device according to the present invention, which is matched with the measurement of a sample two = a substance, includes a sensing chip to absorb the substance and generate a mechanical oscillation; an electronic oscillation circuit, It is electrically connected to the sensing crystal and detects the mass change of the sensing chip caused by the adsorption of the trace substance according to the mechanical vibration f generated by the sensing chip. Two test slots are used to accommodate the sensing chip. The test wafer provides a certain space for measurement. At least one sample inlet is located on the wall of one of the test tanks and is used to place the sample into the test tank. A sample outlet is located in the test tank. The wall of the tank is used as the sample exiting the test tank from the 1220687 mouth; a vacuum pump is connected to the test tank to extract the trace substance attached to the sensing chip; and a temperature controller It is used to control the temperature of the test tank 'for high temperature measurement or desorption of the trace substance during the regeneration of the sensing chip. [Performance method] The quartz crystal microbalance device of the present invention includes a sensing chip that adsorbs a trace amount of material in a sample and can generate a mechanical oscillation; an electronic oscillation circuit, preferably with a feedthrough 〇ugh) is electrically connected to the sensing chip, which measures the change in mass of the sensing chip due to the adsorption of trace substances according to the mechanical oscillation changes generated by the sensing chip; a test slot for containing the sensing The wafer provides a closed space during measurement; a sample inlet on the wall of the test tank is used as the entrance of the sample into the test tank; a sample outlet on the wall of the test tank is used as the sample leaving the test tank. 15 outlet ·,-temperature controller, which controls the temperature of the test tank, for high-temperature measurement, gasification of liquid samples, and regeneration of sensing materials; and a vacuum pump connected to the test to extract The trace amount attached to the sensor. The chip 20 of the present invention, when the π is closed, can be used for static measurement of sample concentration. The injection port is usually liquid, and the temperature controller will vaporize the liquid after the injection. The ^ = ^ port is preferably composed of a needle, a syringe, and a rubber stopper. Inject tincture. The device of the present invention is in the heart of the sample. The sample exit population is usually connected to the gas input and output lines and 9 and preferably includes a flow controller connected to the gas input line to control 2 gas samples into the test tank. Flow rate; more preferably, a valve is installed on the gas input and output pipelines to control the switching of the gas input and output pipelines. The inlet of the test tank of the present invention may be a liquid inlet for static measurement, 5 may also be a gas inlet for dynamic measurement, preferably an inlet having both dynamic and static measurement, and a sample inlet for dynamic and static measurement may also be used. They are independent entrances. In the device of the present invention, the sensing wafer is composed of an electrode coated on both sides of a quartz wafer, the electrode can generate a resonance frequency on the quartz wafer, and a sensing material is coated thereon. The sensing material can be a A ceramic material, an organic material is a sub-material or any composite material to provide a location for absorbing the trace substance. The choice of the sensing material is different depending on the trace substance to be adsorbed. The material of the test tank is not limited, and it is preferably composed of glass or stainless steel. In terms of temperature control, a temperature controller usually adjusts the temperature required by the test tank in a timely manner, such as the test temperature, the desorption temperature, the vaporization temperature of the liquid sample of the pan 15, and it is preferably covered with two heating belts around the gas input pipeline In order to heat the gas into the sample in the pipeline in time. In order to allow your reviewers to better understand the technical content of the present invention, three preferred embodiments are described below. In the following three embodiments, they all use the same device, so they have both dynamic and static measurement and regeneration functions. 20 The device is shown in Figure 1. Example 1: Dynamic measurement The quartz crystal microbalance of the present invention is split. In this example, the dynamic measurement is a trace substance (such as water or methylbenzene) in a gas sample. In this device, the sample is controlled by a flow controller 9 in the gas input line i 10 1220687 a standard source of a fixed concentration, and
流量，其中該樣品為一 試槽5壁上之樣品入口 ： 5刀樣口口内之微量物質會被位於不銹鋼測試槽5内之感測晶 片4表面塗覆之陶瓷材料或有機高分子材料吸附；此感測晶 片4如圖2所示，為一兩面各披覆一層金電極A〗之石英晶片 42所構成，而由於感測晶片4上因金電極“施加之振盪電場 (oscillating electric field)，使感測晶片4内部因反壓電效應 10產生一機械振盪，當感測晶片4因吸附之微量物質而改變質 里時，此機械振盪之頻率亦會隨之改變，該感測晶片4以一 金屬導線體之穿通導引（feed thr〇ugh)6與一位在不銹鋼測 "式抬5外之電子振盪電路10相接，該電子振盪電路1 〇即可將 其共振頻率測定出來，並得知微量物質所被吸附之總量。 15隨後，部分樣品經由不銹鋼測試槽、5壁上之樣品出口 13離開 測忒槽5外，進入氣體輸出管線7中，其中在氣體輸出管線7 上具有一閥門8以控制氣體輸出管線7之開關。 本實施例中之石英晶體微天平裝置亦可包含一加熱帶 2包覆於氣體輸入管線1外圍，以加熱該氣體輸入管線丨内之 20樣品；一溫度控制器14，其同時控制測試槽5與加熱帶2之 溫度’故可作高溫下之量測。 AAM2J靜熊吾測 本發明之石英晶體微天平裝置，在本實施例所用之裝 25置結構與實施例1相同，如圖1所示，功用為一液態樣品之 11 ，量物質之靜態量測’其中本實施例與實施例i之不同為樣 口口輸入與輸出之方法。 樣品之輸入係經由-樣品入口 u進入測試槽5内，而此 樣品入心通常為一注射口，該注射口較佳為由一針頭、 5 -針筒、與一橡皮塞所組成，亦可為一定量之自動注射閥。 而^裝置之氣體輸出管線7通常安裝—閥門8以控制氣體輸 出管線7之開關。當液體樣品經由注射口丨丨定量進入測試槽 5々内，並利用溫度控制器14將該液體樣品氣化時，氣體輸出 &線7之閥門8為關閉，以做定容之量測。其中該注射口 ^ 10可與實施例1之氣體輸入管線1使用同一樣品入口，亦可為 相互獨立之樣品入口，故本裝置可同時具有動靜態量測。 fAM 3 :再生方色 本發明之石英晶體微天平裝置，在本實施例所用之裝 15置結構與實施例1相同，功用為感測晶片之再生方法，其中 該樣品内之微量物質需具可脫附情況下才可使用。本裝置 主要是在吸附測試物質之感測材料飽和時進行再生，其係 配合-真空幫浦15與一溫度控制器14 ;其中真空幫浦15與 測试槽5相通’以在量測結束後抽離附著於感測晶片4之微 20量物質，在此同時，溫度控制器14控制測試槽5之溫度，以 使測試槽5達到脫附微量物質所需之溫度，此時感測晶片4 無須取出於測試槽5外以驅離測試物質。且由於裝置上安裝 真空幫浦15，故可做真空下之氣體待測物質之量測，減少 其他氣體組成成分對待測物質量測之影響。 12 1220687 在S知技藝中’石英晶片上之感測材料被測試物質填 滿後j就必須拆除量測裝置，取出感測晶片置入高溫爐烘 烤將附著在晶片上的測試物質驅離，有時還需配合真空 幫庸抽氣始可達到再生的目的。本實施例中，量測裝置無 5須拆除，即可直接達到再生動作。 …、 綜上所述，本發明結合了動、靜態量測的設計，並且 可以调整測試環境的溫度，更重要的是，不需取出感測晶 片即可做再生的動作，是一套多功能的氣體測試裝置。而 上述實施例僅係為了方便說明而舉例而已，本發明所主張 10之權利範圍自應以申請專利範圍所述為準，而非僅限於二 述實施例。 【圖式簡單說明】 15 圖1係本發明石英晶體微天平裝置一較佳實施例之示意圖。 圖2係本發明石英晶體微天平裝置__較佳實施例之感測晶 片示意圖。 【圖號說明】 1 氣體輸入管線 2 加熱帶 3 4 感測晶片 5 測試槽 6 7 氣體輸出管線 8 閥門 9 10 電子振靈電路 11 樣品入口（注12 射口） 13 樣品出口 14 溫度控制器 15 兩向閥 穿通導引 流量控制器 樣品入口 真空幫浦 13 1220687Flow, where the sample is the sample inlet on the 5 wall of a test cell: The trace material in the 5 knife sample port will be adsorbed by the ceramic material or organic polymer material coated on the surface of the sensing wafer 4 located in the stainless steel test tank 5; As shown in FIG. 2, the sensing wafer 4 is composed of a quartz wafer 42 coated with a layer of gold electrode A on both sides, and because the “oscillating electric field” applied by the gold electrode on the sensing wafer 4, A mechanical oscillation is generated inside the sensing wafer 4 due to the anti-piezoelectric effect 10, and when the sensing wafer 4 changes its mass due to the adsorbed trace substance, the frequency of the mechanical oscillation will also change accordingly. A feed thrugh 6 of a metal wire body is connected to an electronic oscillation circuit 10 outside the stainless steel measuring type 5, and the electronic oscillation circuit 10 can measure its resonance frequency. Then, the total amount of trace substances adsorbed was obtained. 15 Subsequently, some samples left the test tank 5 through the stainless steel test tank, the sample outlet 13 on the wall, and entered the gas output line 7, where the gas output line 7 have A valve 8 is used to control the opening and closing of the gas output line 7. The quartz crystal microbalance device in this embodiment may also include a heating belt 2 surrounding the gas input line 1 to heat 20 samples in the gas input line 丨; A temperature controller 14 which controls the temperature of the test tank 5 and the heating belt 2 at the same time, so it can be used for measurement at high temperature. AAM2J Jingxiongwu measures the quartz crystal microbalance device of the present invention. The structure is the same as that of Example 1. As shown in Figure 1, the function is 11 of a liquid sample, and the static measurement of the substance is' the difference between this embodiment and Example i is the method of input and output of the sample port. Sample The input is through the sample inlet u into the test tank 5, and the sample center is usually an injection port. The injection port is preferably composed of a needle, a 5-syringe, and a rubber stopper. A certain amount of automatic injection valve. And the gas output line 7 of the device is usually installed-valve 8 to control the opening and closing of the gas output line 7. When the liquid sample enters the test tank 5々 quantitatively through the injection port, the temperature control is used. 14 When the liquid sample is gasified, the valve 8 of the gas output & line 7 is closed for constant volume measurement. The injection port ^ 10 can use the same sample inlet as the gas input line 1 of Example 1, It can also be independent sample inlets, so this device can have both dynamic and static measurement. FAM 3: Regenerate square color. The quartz crystal microbalance device of the present invention has the same structure as that of the first device. The function is the regeneration method of the sensing chip, in which the trace substance in the sample can be used only after it can be desorbed. This device is mainly used to regenerate when the sensing material that adsorbs the test substance is saturated, which is a combination of vacuum The pump 15 is connected to a temperature controller 14; the vacuum pump 15 is in communication with the test tank 5 so as to extract the micro-quantity substance attached to the sensing chip 4 after the measurement is completed. At the same time, the temperature controller 14 The temperature of the test tank 5 is controlled so that the test tank 5 reaches a temperature required for desorbing a trace amount of substance. At this time, the sensing wafer 4 does not need to be taken out of the test tank 5 to drive away the test substance. And because the vacuum pump 15 is installed on the device, it can measure the gas to be measured under vacuum, reducing the influence of other gas components on the quality of the test. 12 1220687 In S know-how, after the sensing material on the quartz wafer is filled with the test substance, the measuring device must be removed, the sensing wafer is taken out and placed in a high-temperature furnace to bake, and the test substance attached to the wafer is driven away. Sometimes it is necessary to cooperate with vacuum pumping to achieve the purpose of regeneration. In this embodiment, the measuring device can be directly regenerated without removing the measuring device. ... In summary, the present invention combines the design of dynamic and static measurement, and can adjust the temperature of the test environment. More importantly, it can be regenerated without removing the sensing chip. It is a set of multifunctional Gas testing device. The above embodiments are merely examples for the convenience of description. The scope of rights claimed in the present invention should be based on the scope of the patent application, rather than being limited to the two embodiments. [Brief description of the drawings] 15 FIG. 1 is a schematic diagram of a preferred embodiment of the quartz crystal microbalance device of the present invention. Fig. 2 is a schematic diagram of a sensing crystal of a preferred embodiment of a quartz crystal microbalance device of the present invention. [Illustration of drawing number] 1 gas input line 2 heating belt 3 4 sensor chip 5 test slot 6 7 gas output line 8 valve 9 10 electronic vibration circuit 11 sample inlet (note 12 injection port) 13 sample outlet 14 temperature controller 15 Two-way valve through pilot flow controller sample inlet vacuum pump 13 1220687