TWI678532B

TWI678532B - Carbon hydrogen sensor and preparation method and element thereof

Info

Publication number: TWI678532B
Application number: TW104135690A
Authority: TW
Inventors: 徐鎮; Chen Hsu
Original assignee: 徐鎮; Chen Hsu
Priority date: 2015-10-30
Filing date: 2015-10-30
Publication date: 2019-12-01
Also published as: TW201715230A

Abstract

本創作係關於一種可在室溫和高溫下進行碳氫氣感測的感測器，係包括：控制電路模組、顯示模組、感測模組、警示模組和電源模組所組成，以過飽和碳吸附和感測碳氫氣。 This creation is about a sensor that can perform carbon and hydrogen sensing at room temperature and high temperature. It consists of: a control circuit module, a display module, a sensing module, a warning module and a power module. Carbon adsorbs and senses carbon and hydrogen.

Description

一種碳氫氣感測器及其製備方法和元件 Carbon-hydrogen sensor and preparation method and component thereof

本創作係關於一種可在室溫和高溫下進行碳氫氣感測的感測器，係包括：控制電路模組、顯示模組、感測模組、警示模組和電源模組所組成，以過飽和碳吸附碳氫氣。 This creation is about a sensor that can perform carbon and hydrogen sensing at room temperature and high temperature. It consists of: a control circuit module, a display module, a sensing module, a warning module and a power module. Carbon adsorbs carbon hydrogen.

一般傳統氣體感測器依作用原理，可分為半導體式、觸媒燃燒式、電化學式和紅外線感測式等。 Generally, conventional gas sensors can be classified into semiconductor type, catalytic combustion type, electrochemical type, and infrared sensing type according to the principle of action.

半導體式係運用金屬氧化材料燒結成N型半導體，內部纏繞白金電阻絲當成感測器，加熱至300℃，當空氣中只有純氧時，因氧氣接觸產生之負離子與N型半導體之負離子等量，阻抗較大，不易導電.當空氣中碰觸可燃性或毒性物質時，因異性濃度大，相當使氧氣降低，負離子相對減少，阻抗變小，較易導電，形成電子流，檢測出電子流強度即可知濃度多寡。 The semiconductor type uses metal oxide materials to sinter into N-type semiconductors. The internally wound platinum resistance wire is used as a sensor and heated to 300 ° C. When there is pure oxygen in the air, the negative ions generated by oxygen contact are equal to the negative ions of N-type semiconductors. , The impedance is large, it is not easy to conduct electricity. When the flammable or toxic substances are touched in the air, due to the large concentration of the opposite sex, the oxygen is reduced considerably, the negative ions are relatively reduced, the impedance is reduced, it is easier to conduct electricity, and an electron flow is detected. The intensity can tell the concentration.

觸媒燃燒式係運用燃燒量多寡來測定氣體濃度，利用矽纖維成形器纏繞白金電熱絲，熱絲線徑一般為0.03mm左右，一定長度，再用鋁合金灌入成為珠子形狀，外圍塗滿觸媒，來接觸外圍空氣反應熱。當白金絲通入一定電流約200-300mA，其電阻約為2-30歐姆。當電壓約為1.5~5.0V，此時為維持一定溫度約為300~500℃以幫助反應。當在空氣中時，一定氧氣即保持一定電流。當空氣與可燃性氣體混合時，可燃性氣體被氧化與觸媒接觸產生燃燒熱，使白金絲表面溫度上升，因金屬特性，溫度越高電阻就越大，若通以電流則相對減少。故利用惠斯登橋將極小電阻之變化測出，加以放大，即可得可燃性氣體之濃度量。 The catalytic combustion system uses the amount of combustion to measure the gas concentration. A silicon fiber shaper is used to wind a platinum electric heating wire. The diameter of the heating wire is generally about 0.03mm. A certain length is filled with aluminum alloy to form a bead shape. Medium to come into contact with the surrounding air to react to the heat. When the platinum wire passes a certain current of about 200-300mA, its resistance is about 2-30 ohms. When the voltage is about 1.5 ~ 5.0V, at this time to maintain a certain temperature of about 300 ~ 500 ℃ to help the reaction. When in the air At this time, a certain amount of oxygen maintains a certain current. When air is mixed with a flammable gas, the flammable gas is oxidized and comes into contact with the catalyst to generate combustion heat, which causes the surface temperature of the platinum wire to rise. Due to the characteristics of the metal, the higher the temperature, the greater the resistance, and the lower the current flow. Therefore, use Wheatstone bridge to measure the change of the minimum resistance and enlarge it to get the concentration of flammable gas.

電化學式以隔膜電極式為例，隔膜電極原理係以酸鹼值PH之變化，測量氧氣存量。兩電極分別浸潤於電解液中，經過0.4mm鐵氟龍篩子孔型膜片，當做介質隔膜，此隔膜具有透氣性，空氣中的氧含量多寡，而透入電解液中，使電解液產生酸鹼變化，直接影響氫氧分子離基，使電流形成環路，但此為極小電流。配合高阻抗放大器.將信號放大即可辨別氧氣含量多寡。主要測量為0₂，毒性之Cl₂、NH₃、H₂S...等。 The electrochemical formula takes the diaphragm electrode type as an example. The principle of the diaphragm electrode is based on the change in the pH value of pH to measure the oxygen storage. The two electrodes are immersed in the electrolyte, and pass through a 0.4mm Teflon sieve aperture membrane as a dielectric diaphragm. This diaphragm is breathable and has a large amount of oxygen in the air. It penetrates into the electrolyte and causes the electrolyte to generate acid The change of the base directly affects the radical separation of the hydrogen and oxygen molecules, causing the current to form a loop, but this is a very small current. With high-impedance amplifier, you can distinguish the oxygen content by amplifying the signal. The main measurement is 0 ₂ , toxic Cl ₂ , NH ₃ , H ₂ S, etc.

紅外線感測式係運用任何氣體經能源激放會產生溫度，位移或頻率變化，而其軌道有規律可循，對可燃性氣體而言，使用紅外線照射，當照射後被氣體吸收的程度，來判斷有無碳氫含量多寡，當研究出其波長吸收曲線後，可即定性，亦可定量。 Infrared sensing is the use of any gas to generate temperature, displacement or frequency changes when excited by energy, and its orbit can be followed regularly. For flammable gases, infrared radiation is used, and the degree of absorption by the gas after irradiation. Determine whether the content of hydrocarbons is high or low. When the wavelength absorption curve is studied, it can be qualitative or quantitative.

其中適合碳氫氣體傳感器的紅外線感測應用中，由於它們的系統較複雜，品質不易控制。有鑑於此，本案之創作人搭配自身的創意及不斷的嘗試下，進而研發出一種可有效改善降低這個缺點，改善上述習知技術中所提及的缺憾，發展出一種之室溫和高溫可感測碳氫氣的感測器。 Among them, infrared sensors suitable for hydrocarbon gas sensors are difficult to control due to their complicated systems. In view of this, the creators of this case, with their own creativity and continuous attempts, have developed a method that can effectively improve and reduce this shortcoming, improve the defects mentioned in the above-mentioned conventional technology, and develop a kind of room temperature and high temperature sensible Carbon and hydrogen sensor.

本創作之主要目的，乃在於提出本創作係關於一種可在室溫和高溫下進行碳氫感測的感測器，係包括：控制電路模組010、顯示模組020、感測模組030、警示模組040和電源模組050所組成。藉由過飽和碳吸附氫氣，和通過檢測電流時間檢測氫氣的濃度，其運作方式與傳統感測碳氫氣不同，可迅速達到碳氫氣感測的目的。 The main purpose of this creation is to propose that this creation is about a sensor that can perform hydrocarbon sensing at room temperature and high temperature, including: control circuit module 010, display module 020, sensing module 030, It consists of a warning module 040 and a power module 050. By supersaturated carbon adsorption Attaching hydrogen, and detecting the concentration of hydrogen by detecting the current time, its operation mode is different from the traditional sensing of carbon and hydrogen, which can quickly achieve the purpose of carbon and hydrogen sensing.

010‧‧‧控制電路模組 010‧‧‧Control circuit module

020‧‧‧顯示模組 020‧‧‧Display Module

030‧‧‧感測模組 030‧‧‧Sensor Module

040‧‧‧警示模組 040‧‧‧Warning Module

050‧‧‧電源模組 050‧‧‧Power Module

第1圖係為本創作之感測器之示意圖。 Figure 1 is a schematic diagram of the sensor for this creation.

第2圖係為本創作之氫感測模組成分的碳/鋅成分圖。不同配方之碳/鋅(C/Zn)值。比例(1：2)所得之草酸鋅C/Zn<2未飽和，比例(1：1)所得之草酸鋅C/Zn>2過飽和，比例(1：0.5)所得之草酸鋅C/Zn<2未飽和。 Figure 2 is a carbon / zinc composition diagram of the hydrogen sensing module composition of this creation. Carbon / zinc (C / Zn) values for different formulations. The ratio of zinc oxalate C / Zn <2 unsaturated in ratio (1: 2), the ratio of zinc oxalate C / Zn> 2 obtained in ratio (1: 1) is supersaturated, and the ratio of zinc oxalate C / Zn <2 obtained in ratio (1: 0.5) Not saturated.

第3圖係為常溫(25℃)和高溫(150℃)下，各種氣體之響應的選擇性，對於碳氫氣有較佳的選擇性。 Figure 3 shows the selectivity of the response of various gases at normal temperature (25 ° C) and high temperature (150 ° C), with better selectivity for carbon and hydrogen.

第4圖係為本創作常溫(25℃)和高溫(150℃)下的回復時間。 Fig. 4 is the recovery time of this creation at normal temperature (25 ° C) and high temperature (150 ° C).

為了能夠更清楚地描述本創作所提出之一種感測器，以下將配合圖示，詳盡說明本創作之較佳實施例。請參閱第1圖，係本創作之感測器示意圖，係包括：一控制電路模組010，一顯示模組020，一感測模組030，一警示模組040和一電源模組050。 In order to more clearly describe a sensor proposed in this creation, the preferred embodiment of this creation will be described in detail below with reference to the drawings. Please refer to FIG. 1, which is a schematic diagram of the sensor of this creation, including: a control circuit module 010, a display module 020, a sensing module 030, a warning module 040 and a power module 050.

本創作之感測器之實施例過程如下：依比例將醋酸鋅加入甲醇溶液，配置醋酸鋅甲醇溶液，然後進行凝膠法。另，加入製備還原氧化石墨烯粉末，以超音波震盪機震盪，再以微量離心機離心後取出並清洗，之後將取出離心物放置烘箱時間放置一段時間，最後取出製備之草酸鋅粉末，然後進行雷射凝結成膜，再結合電路後進行各項測試。 An example process of the sensor of this creation is as follows: zinc acetate is added to a methanol solution in proportion, a zinc acetate methanol solution is configured, and then a gel method is performed. In addition, the prepared reduced graphene oxide powder is added, oscillated with an ultrasonic oscillator, centrifuged in a microcentrifuge and taken out and washed, and then the centrifuged material is placed in an oven for a period of time, and finally the prepared zinc oxalate powder is taken out, and then The laser is condensed to form a film, and then combined with the circuit, various tests are performed.

請參閱第2圖，係本創作之感測模組成份圖，該成份圖係運用能量發散光譜儀EDS分析大區域面積範圍下的元素組成。EDS是利用電子束將試片中元素內層的電子擊出，並由較外層的電子回填空出的電子軌域，因此會放出代表該元素特性X光，特性X光是當高能量的電子入射材料內的原子時，低能階的電子被激發而脫離原子核的束縛，而高能階的電子回填至低能階所產生的X光。雙前驅物之凝膠法還原氧化石墨烯/氧化鋅RGO/ZnO比例(1：2)；RGO/ZnO比例(1：1)；RGO/ZnO比例(1：0.5)所偵測的結果，製備出含碳之草酸鋅。 Please refer to Figure 2, which is the composition diagram of the sensor module created in this article. Elemental composition in a large area was analyzed by energy dispersive spectrometer EDS. EDS uses electron beams to knock out the electrons in the inner layer of the element in the test strip, and backfills the empty electron orbital regions with the outer electrons. Therefore, X-rays that are characteristic of the element are emitted. When atoms in the material are incident, low-level electrons are excited and free from the nucleus of the atom, while high-level electrons are backfilled to the X-rays generated by the low-level electrons. Double precursor precursor gel method to reduce graphene oxide / zinc oxide RGO / ZnO ratio (1: 2); RGO / ZnO ratio (1: 1); RGO / ZnO ratio (1: 0.5). Out of carbon zinc oxalate.

請參閱第3圖，係為本創作常溫(25℃)下過飽和碳之草酸鋅對各種氣體的感測測結果圖，碳氫氣響應明顯增加，且隨時間增加而持續上升。但對於O₂氧氣和N₂氮氣則無明顯變化。 Please refer to Figure 3, which is a graph of sensing results of various gases by zinc oxalate with supersaturated carbon at normal temperature (25 ° C). The carbon and hydrogen response increased significantly and continued to increase with time. However, there was no significant change for O ₂ oxygen and N ₂ nitrogen.

請參閱第4圖，係為本創作常溫(25℃)和高溫(150℃)下的回復時間圖。在室溫下可在數十分鐘內回復近75%左右，在高溫下則可完全回復。 Please refer to Figure 4, which is a graph of the recovery time at normal temperature (25 ° C) and high temperature (150 ° C). At room temperature, it can recover nearly 75% in tens of minutes, and it can completely recover at high temperature.

上述已對本創作之結構和特性做了詳細的描述，由本創作可知本創作之優點係可於室溫和高溫下進行碳氫氣感測，並可迅速回復原始狀態之優點。然而，上述之詳細說明係針對本創作可行較佳實施例之具體說明，惟該實施例並非用以限制本創作之專利範圍，凡未脫離本創作技藝精神所為之等效實施或變更，均應包含於本案之專利範圍中。 The structure and characteristics of this creation have been described in detail above. From this creation, it can be seen that the advantages of this creation are the advantages of carbon and hydrogen sensing at room temperature and high temperature, and the original state can be quickly restored. However, the above detailed description is a specific description of a feasible and preferred embodiment of this creation, but this embodiment is not intended to limit the scope of the patent for this creation. Any equivalent implementation or change that does not depart from the spirit of this creation technique should be Included in the patent scope of this case.

Claims

一種碳氫氣感測器，以草酸鋅電阻感測技術為主，在韌體和硬體上能在室溫下感測、顯示、控制、和警示草酸鋅電阻值並能反應出甲烷碳氫氣為目標，硬體上係包含：一控制電路模組，係處理碳氫感測所需之訊號電路模組，將感測訊號進行處理、顯示和警示；一顯示模組，係顯示碳氫感測資訊之模組，將感測模組訊號顯示於顯示模組，連接於控制電路模組；一感測模組，係感測碳氫氣之感測模組，提供碳氫氣感測訊號，連接於控制電路模組；一警示模組，係警示碳氫氣感測之模組，當感測到碳氫分子時和碳氫分子濃度值達一數值，發出警示作用，連接於控制電路模組；一電源模組，係提供碳氫氣感測器所需之電源，連接提供各模組所需之電力；可在室溫下，以合成之草酸鋅吸附甲烷碳氫氣，進行碳氫氣感測。A carbon hydrogen sensor based on zinc oxalate resistance sensing technology, which can sense, display, control, and warn the resistance value of zinc oxalate on firmware and hardware at room temperature and can reflect methane carbon hydrogen as The target includes on the hardware: a control circuit module, which is a signal circuit module for processing hydrocarbon sensing, and processes, displays, and alerts the sensing signal; a display module, which displays hydrocarbon sensing The information module displays the signal of the sensing module on the display module and is connected to the control circuit module. A sensing module is a sensing module that senses carbon and hydrogen and provides a carbon and hydrogen sensing signal. Control circuit module; a warning module, which is a module that warns of carbon and hydrogen sensing. When a hydrocarbon molecule is detected and the concentration value of the hydrocarbon molecule reaches a value, it issues a warning function and is connected to the control circuit module; The power module is used to provide the power required by the carbon and hydrogen sensors, and connected to provide the power required by each module. At room temperature, the synthesized zinc oxalate can be used to adsorb methane, carbon and hydrogen for carbon and hydrogen sensing.

一種碳氫氣感測器，以草酸鋅電阻感測技術為主，在韌體和硬體上能在硬體上能在高溫50℃以上感測、顯示、控制、和警示之草酸鋅電阻值並能反應出甲烷碳氫氣濃度為目標，硬體上係包含：一控制電路模組，係處理碳氫氣感測之訊號電路模組，將感測訊號進行處理、顯示和警示；一顯示模組，係顯示碳氫氣感測資訊之模組，將感測模組訊號顯示於顯示模組，連接於控制電路模組；一感測模組，係感測碳氫氣之感測模組，提供碳氫氫感測訊號，連接於控制電路模組；一警示模組，係警示碳氫氣感測之模組，當感測到碳氫氣時和碳氫氣濃度值達一數值，發出警示作用，連接於控制電路模組；一電源模組，係提供碳氫氣感測器所需之電源，連接提供各模組所需之電力；可在高溫50℃以上，以吸附合成之草酸鋅碳氫氣，進行碳氫氣感測。A carbon hydrogen sensor based on zinc oxalate resistance sensing technology, which can sense, display, control, and warn the resistance value of zinc oxalate on the firmware and hardware on the hardware at a high temperature of 50 ° C and above. It can reflect the concentration of methane, carbon, and hydrogen as the target. The hardware includes: a control circuit module, which is a signal circuit module that processes carbon and hydrogen sensing, and processes, displays, and alerts the sensing signal; a display module, It is a module that displays carbon and hydrogen sensing information. The signal of the sensing module is displayed on the display module and connected to the control circuit module. A sensing module is a sensing module that detects carbon and hydrogen to provide hydrocarbons. A hydrogen sensing signal is connected to the control circuit module; a warning module is a module that warns of carbon and hydrogen sensing. When carbon and hydrogen are sensed, the value of the carbon and hydrogen concentration reaches a value, and it sends a warning function, and is connected to the control. Circuit module; a power module, which provides the power required by the carbon and hydrogen sensors, and provides the power required by each module; can be used at a high temperature above 50 ° C to adsorb the synthesized zinc oxalate carbon hydrogen to perform carbon hydrogen Sensing.

一種碳氫氣感測器，以草酸鋅電阻感測技術為主，在韌體和硬體上能在硬體上能在室溫和高溫50℃以上感測、顯示、控制、和警示之草酸鋅電阻值並能以吸附訊號產生之時間，計算甲烷碳氫氣體含量為目標，硬體上係包含：一控制電路模組，係處理碳氫氣資訊之模組，將感測模組訊號進行處理、顯示和警示；一顯示模組，係顯示碳氫氣感測資訊之模組，將感測模組訊號顯示於顯示模組，連接於控制電路模組；一感測模組，係感測碳氫氣之感測模組，提供碳氫氣感測訊號，連接於控制電路模組；一警示模組，係警示碳氫氣感測之模組，當感測到碳氫分子時和碳氫分子濃度值達一數值，發出警示作用，連接於控制電路模組；一電源模組，係提供碳氫氣感測器所需之電源，連接提供各模組所需之電力；進行碳氫甲烷氣體感測，運用吸附訊號產生之時間，計算碳氫甲烷氣體含量。A carbon hydrogen sensor based on zinc oxalate resistance sensing technology, which can detect, display, control, and warn zinc oxalate resistance on the firmware and hardware at room temperature and high temperature above 50 ° C. The value can be based on the time when the adsorption signal is generated and calculate the methane hydrocarbon content. The hardware includes: a control circuit module, a module that processes the carbon and hydrogen information, and processes and displays the signal of the sensing module. And warning; a display module, which is a module that displays carbon and hydrogen sensing information, displays the signal of the sensing module on the display module and is connected to the control circuit module; a sensing module, which is a sensor that detects carbon and hydrogen The sensing module provides carbon and hydrogen sensing signals and is connected to the control circuit module. An alert module is a module that alerts carbon and hydrogen sensing. When a hydrocarbon molecule is sensed, the concentration value of the hydrocarbon molecule reaches one. Numerical value, issued a warning function, connected to the control circuit module; a power module, which provides the power required by the carbon and hydrogen sensors, connected to provide the power required by each module; perform hydrocarbon methane sensing, use adsorption When the signal was generated, Operators hydrocarbon content of methane gas.

一種碳氫氣感測元件，係感測碳氫氣之感測元件，該元件為一草酸鋅，可於室溫下感測甲烷碳氫氣。A carbon-hydrogen sensing element is a sensing element that senses carbon-hydrogen. The element is zinc oxalate and can detect methane, carbon-hydrogen, and hydrogen at room temperature.

一種碳氫氣感測元件，係感測碳氫分子之感測元件，為一草酸鋅，可於高溫50℃以上感測甲烷碳氫氣。A carbon-hydrogen sensing element is a sensing element that senses hydrocarbon molecules. It is zinc oxalate and can detect methane, carbon and hydrogen at a high temperature above 50 ° C.

一種碳氫氣感測元件之構成粉末，係由溶膠凝膠法製備，採石墨烯和氧化鋅雙前驅物經合雷射加工成草酸鋅製備而成。A constituent powder of a carbon-hydrogen sensing element is prepared by a sol-gel method, and a graphene and a zinc oxide double precursor are processed by laser to zinc oxalate.

一種碳氫氣感測元件之感測膜，係採用石墨烯和氧化鋅雙前驅物的溶膠凝膠法經雷射加工後製成草酸鋅薄膜。A sensing film for a carbon-hydrogen sensing element is a sol-gel method using graphene and zinc oxide double precursors after laser processing to form a zinc oxalate film.