阅读说明：本技术 一种具有尾气感测装置的船舶机构 (Ship mechanism with tail gas sensing device ) 是由 马强 刘刚 郭俊杰 徐海东 王明雨 孙庶业 李晓 侯甲彬 于 2019-10-23 设计创作，主要内容包括：目前船舶尾气的排放标准朝着规范化,严格化方向发展,但是检测设备体积大,检测工作量大、不方便,迫切需要改变这一现状,本发明的尾气感测装置具有纳米感测元件,纳米感测元件能够对船舶尾气中的甲烷等污染气体进行感测,其中,纳米感测元件包含氧化锌纳米柱,不仅检测方便,成本低廉,同时数值采集准确,稳定可靠,制作成本低,作用显著增强,也大大提高了整体的高效性和操作的可靠性。(The tail gas sensing device is provided with a nano sensing element, the nano sensing element can sense polluted gases such as methane in the tail gas of the ship, and the nano sensing element comprises a zinc oxide nano column, so that the tail gas sensing device is convenient to detect, low in cost, accurate in numerical value acquisition, stable and reliable, low in manufacturing cost, remarkably enhanced in effect, and greatly improved in overall efficiency and operation reliability.)

1. The utility model provides a marine mechanism with tail gas sensing device, marine mechanism include hull, hull skeleton, deck, cabin, superstructure, a serial communication port, marine mechanism still include tail gas sensing device, tail gas sensing device nanometer sensing element has, nanometer sensing element can carry out the sensing to the gaseous pollutants in the ship's tail gas, wherein, nanometer sensing element contain zinc oxide nano-column, zinc oxide nano-column form by following technology preparation:

in the first step, the substrate is cut,

step two, a yellow light process;

thirdly, magnetron sputtering;

fourthly, removing the photoresist;

and fifthly, carrying out hydro-thermal synthesis.

2. The marine structure with an exhaust gas sensor according to claim 1, wherein the substrate is a 188 μm thick PET film cut to 1.5cm x1.5cm, and the protective film is torn off for use without cleaning.

3. The marine structure with an exhaust gas sensor according to claim 1 or 2, wherein in the yellow light process, firstly, the photoresist is uniformly coated on the surface of the substrate by using a spin coater, and the coating is performed at two rotation speeds, wherein the first rotation speed is 500rpm, the spin coating time is 10 seconds, the second rotation speed is 1300rpm, and the spin coating time is 20 seconds; then, soft baking for 90 seconds to enable the positive photoresist to become a solid film and be attached to the substrate; then, irradiating the substrate with the photoresist by using an exposure machine to transfer the pattern on the photomask to the substrate; finally, the diluted developer is used for removing the redundant photoresist to form a first blank.

4. The marine vessel structure with an exhaust gas sensor as claimed in claim 3, wherein during the magnetron sputtering process, a magnetron RF sputtering system is used to sputter a layer of ZnO film with a thickness of 180nm onto the photoresist on the first blank at room temperature to form a second blank, wherein the magnetron RF sputtering system includes a vacuum chamber, a rotating table is disposed in the vacuum chamber, the blank can be placed on the rotating table and can rotate along with the rotating table, a target assembly is disposed above the rotating table, a ZnO target is disposed on the target assembly, an RF instrument can provide RF energy to the target assembly, the upper portion of the vacuum chamber is further communicated with the Ar gas cylinder through a pipeline channel, and a flow control valve is further disposed on the pipeline channel.

5. The marine structure with an exhaust gas sensor according to claim 1, wherein in the photoresist removing process, the second blank is placed in acetone for standing, after the color of the photoresist of the second blank disappears completely and becomes a transparent ZnO film, the second blank is cleaned by DI water and dried by a nitrogen gun to form a third blank.

6. The marine mechanism with the exhaust gas sensing device according to claim 1, wherein in the hydrothermal synthesis process, the third blank is placed into a hydrothermal reaction pressure kettle, 20ml of 20% hexamethylenetetramine and 20ml of 20% zinc acetate dihydrate are poured, and after the reaction at 95 ℃ for 5.5 hours, the third blank is naturally cooled to form the zinc oxide nano-column.

7. A light measuring device of a gas sensing element, the gas sensing element comprises a zinc oxide nano column, the zinc oxide nano column is prepared by any one process of claims 1 to 7, and the light measuring device is characterized in that the light measuring system comprises a measuring aluminum box, a measuring base is arranged in the measuring aluminum box, a light-transmitting window is arranged at the upper part of the measuring aluminum box, a UV/LED light source can irradiate the measuring base through the light-transmitting window, the light measuring system further comprises a measuring ammeter, and the measuring ammeter is connected with a computer.

8. A use method of a gas measurement system, the gas measurement system is composed of the optical measurement device of the gas sensing element of claim 7, characterized in that, when the optical measurement device of the gas sensing element is used, the zinc oxide nano-pillar is placed on a circuit board, then the zinc oxide nano-pillar is connected with an upper electrode by conductive silver paste, the connected circuit board is fixed on a measurement base, then the connected circuit board is connected to an ammeter by a circuit, the distance between the zinc oxide nano-pillar on the circuit board and a light source is 1.3cm, and a measurement aluminum box is in a closed state during the measurement and the photometry.

9. A gas measuring device of a gas sensing element, the gas sensing element comprises a zinc oxide nano column, the zinc oxide nano column is prepared by any one process of claims 1 to 7, the gas measuring device comprises a measuring chamber, a measuring base is arranged in the measuring chamber, the measuring chamber is respectively connected with an air steel cylinder and a gas steel cylinder to be measured through a measuring pipeline, a flow control valve is further arranged on the measuring pipeline, the gas measuring device further comprises a measuring ammeter, the measuring ammeter is connected with a computer, the gas measuring device further comprises a UV light source frame, the UV light source frame is arranged outside a transparent glass cover and is fixed by a support, wherein the measuring chamber is composed of a transparent glass cover, and the diameter of the transparent glass cover is about 13 cm.

10. A method of using a gas measuring system constituted by the gas measuring apparatus of a gas sensor element according to claim 9, characterized in that the method of using the gas measuring apparatus of a gas sensor element is as follows: the method comprises the steps of placing a zinc oxide nano column on a circuit board, connecting the zinc oxide nano column with an upper electrode by using conductive silver adhesive, fixing the connected circuit board in the center of a measuring base, connecting a circuit of the circuit board to an ammeter, arranging the measuring base in the center of a transparent glass cover, controlling respective flow of an air steel cylinder and a gas steel cylinder to be measured by a flow control valve so as to calculate gas concentration, and converging the gas steel cylinder and the gas steel cylinder into the same pipeline to flow into the transparent glass cover.

Technical Field

The invention relates to the field of ship environment protection, in particular to a ship mechanism with an exhaust gas sensing device.

Background

In many cases, the direct discharge of ship exhaust gas has a serious adverse effect on the atmospheric quality in many port cities and inland river regions. The marine diesel engine has the characteristics of high fluidity, high diffusivity and long duration, and the main pollutants discharged by the marine diesel engine comprise nitrogen oxides, sulfur oxides, carbon-chlorine compounds, particles and the like. As a result, the exhaust gas from ships contains dozens of strong carcinogenic chemical substances, and the health of coastal residents is affected by environmental pollution.

The first work to be done is to accurately detect the emissions in order to control the pollution in water areas such as river channels. The development of equipment which can meet the current emission regulation and detection regulation and can quickly detect the automobile exhaust emission is imperative. However, the marine exhaust gas sensing device is complex and expensive, so that a marine mechanism with the exhaust gas sensing device is urgently needed to meet practical needs.

Disclosure of Invention

Accordingly, in view of the disadvantages in the related art, examples of the present invention are provided to substantially solve one or more problems due to limitations and disadvantages of the related art, to substantially improve safety and reliability, and to effectively protect equipment.

According to the technical scheme provided by the invention, the invention discloses a ship mechanism with an exhaust gas sensing device, and the ship mechanism comprises a ship shell, a ship body framework, a deck, a cabin and an superstructure.

The marine mechanism further comprises a tail gas sensing device, the tail gas sensing device is provided with a nano sensing element, the nano sensing element can sense the polluted gas in the marine tail gas, wherein the nano sensing element comprises a zinc oxide nano column, and the zinc oxide nano column is prepared by the following process:

in the first step, the substrate is cut,

step two, a yellow light process;

thirdly, magnetron sputtering;

fourthly, removing the photoresist;

and fifthly, carrying out hydro-thermal synthesis.

Further, the substrate was a 188 μm thick PET film cut to a size of 1.5cmx1.5cm, and the protective film was used by tearing it off without cleaning.

Further, in the yellow light manufacturing process, firstly, a spin coater is utilized to uniformly coat the positive photoresist on the surface of the substrate, and two rotating speeds are respectively and sequentially coated, wherein the first rotating speed is 500rpm, the spin coating time is 10 seconds, the second rotating speed is 1300rpm, and the spin coating time is 20 seconds; then, soft baking for 90 seconds to enable the positive photoresist to become a solid film and be attached to the substrate; then, irradiating the substrate with the photoresist by using an exposure machine to transfer the pattern on the photomask to the substrate; finally, the diluted developer is used for removing the redundant photoresist to form a first blank.

Further, in the magnetron sputtering process, a layer of ZnO film with the thickness of 180nm is sputtered on the photoresist on the first blank by using a magnetron radio frequency sputtering system at room temperature to form a second blank, wherein the magnetron radio frequency sputtering system comprises a vacuum chamber, a rotating table is arranged in the vacuum chamber, the blank can be placed on the rotating table and can rotate along with the rotating table, a target assembly is arranged above the rotating table, a ZnO target is arranged on the target assembly, a radio frequency instrument can provide RF energy for the target assembly, the upper part of the vacuum chamber is also communicated with an Ar gas cylinder through a pipeline channel, and a flow control valve is also arranged on the pipeline channel.

Further, in the photoresist removing process, the second blank is placed into acetone for standing, after the color of the photoresist of the second blank disappears completely and becomes a transparent ZnO film, the second blank is cleaned by DI water and dried by a nitrogen gun to form a third blank.

Further, in the hydrothermal synthesis process, the third blank is placed into a hydrothermal reaction pressure kettle, and 20ml of 20% hexamethylene tetramine and 20ml of 20% zinc acetate dihydrate are poured. Reacting at 95 ℃ for 5.5 hours, and then naturally cooling to form the zinc oxide nano-column.

The invention also discloses a light measuring device of the gas sensing element, the gas sensing element comprises a zinc oxide nano column, the zinc oxide nano column is prepared by the process, the light measuring system comprises a measuring aluminum box, a measuring base is arranged in the measuring aluminum box, a light-transmitting window is arranged at the upper part of the measuring aluminum box, the UV/LED light source can irradiate the measuring base through the light-transmitting window, and the light measuring system also comprises a measuring ammeter which is connected with a computer.

The invention also discloses a gas measuring device of the gas sensing element, the gas sensing element comprises a zinc oxide nano column, the zinc oxide nano column is prepared by the process, the gas measuring device comprises a measuring cavity, a measuring base is arranged in the measuring cavity, the measuring cavity is respectively connected with an air steel cylinder and a gas steel cylinder to be measured through a measuring pipeline, a flow control valve is also arranged on the measuring pipeline, the gas measuring device also comprises a measuring ammeter, the measuring ammeter is connected with a computer, the gas measuring device also comprises a UV light source frame, the UV light source frame is arranged outside the transparent glass cover and is fixed by a support, wherein the measuring cavity is composed of a transparent glass cover, and the diameter of the transparent glass cover is about 13 cm.

At present, the emission standard of ship tail gas is developed towards standardization and strictness, but the detection equipment is large in size, and the detection workload is large and inconvenient. The tail gas sensing device is provided with a nano sensing element, the nano sensing element can sense polluted gases such as methane in the tail gas of the ship, and the nano sensing element comprises a zinc oxide nano column, so that the tail gas sensing device is convenient to detect, low in cost, accurate in numerical value acquisition, stable and reliable, low in manufacturing cost, remarkably enhanced in effect, and greatly improved in overall efficiency and operation reliability.

Drawings

FIG. 1 is a schematic diagram of a zinc oxide nano-column preparation device of the present invention.

FIG. 2 is a schematic diagram of the preparation process of the zinc oxide nano-pillar of the invention.

FIG. 3 is a schematic view of a magnetron RF sputtering system according to the present invention.

FIG. 4 is a schematic view of an optical measuring device of the gas sensor of the present invention.

FIG. 5 is a schematic view of a gas measuring device of the gas sensor device of the present invention.

Detailed Description

The present invention will be further described with reference to the following specific examples.

The present invention will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.

The application of the principles of the present invention will be further described with reference to the accompanying drawings and specific embodiments. With the rapid development of the industry, the air pollution problem has been gradually valued by the public in severity in recent years. The air pollution is various and may be gas, aerosol, etc., and the so-called air pollution generally causes negative effects on human bodies or ecological environment. Especially for ships, and the influence of ship exhaust gas is extremely easy to ignore.

The gas sensor has a wide application field, and in recent years, due to the increasing environmental pollution and the rising health consciousness, the market demand is continuously increased, and many people in the research field continuously put into efforts for a gas sensor which is faster and more sensitive and can simultaneously detect a plurality of gases. Among them, a gas sensor made of Metal Oxide (MOS) has been widely used since the advent because of its high sensitivity, low material cost, easy fabrication of components, small size, high heat resistance, and the like. In recent years, as nano-sized structures have been widely studied, the sensitivity of gas sensors has been remarkably improved with a greatly increased body surface area. The invention uses the yellow light technology to match with the excellent gas permeability and high surface area to volume ratio of the nano-column, greatly increases the surface area which can be absorbed by gas compared with the common old film type gas sensor, and achieves the purpose of high sensitivity.

As nanostructures have been extensively studied in recent years, nanostructured ZnO has been demonstrated to have significantly improved sensitivity due to its greater surface area to volume ratio. The ZnO nano-column, the nano-wire and other nano-structures have different sensitivities to nitric oxide, nitrogen dioxide, methane, acetone, carbon monoxide, hydrogen and water gas because of different manufacturing methods and structures.

The MOS material can be divided into N-type according to its majority carrier(N-type), P-type, N-type semiconductors such as SnO₂、TiO₂The ZnO majority carrier is an electron and conducts electricity by the electron on the conduction band, and the P-type semiconductor such as GaN and PbS majority carrier is a hole and conducts electricity by the movement of the hole. When the gas is adsorbed and desorbed on the surface of the semiconductor, the resistance of the material changes, and the sensing purpose can be achieved. The gas to be measured is divided into oxidizing gas and reducing gas, and the change direction of the resistance is different according to the difference of the main carrier of the semiconductor and the difference of the gas.

When the N-type oxide semiconductor is exposed to an oxidizing gas, electrons on the surface of the semiconductor are trapped and cannot move due to adsorption of the oxidizing gas, which increases the resistance. In contrast, in the case of a P-type oxide semiconductor, surface electrons are trapped, and the concentration of holes increases, which results in a decrease in resistance.

The manufacturing process of the zinc oxide nano-column gas sensor is shown in figure 1-2. The method comprises five steps, namely a first step of cutting a substrate, a second step of performing a yellow light process; thirdly, magnetron sputtering; fourthly, removing the photoresist; and fifthly, carrying out hydro-thermal synthesis.

The substrate of the invention is cut into a size of 1.5cmx1.5cm by using a 188-micron-thick PET film, and the protective film is torn off for use without cleaning.

The photolithography process of the present invention is divided into three parts, which are photoresist coating, exposure and development in sequence.

Firstly, uniformly coating a positive photoresist (EPG510) on the surface of a substrate by using a spin coater, and respectively coating at two rotating speeds in sequence, wherein the first rotating speed is 500rpm, the spin coating time is 10 seconds, the second rotating speed is 1300rpm, and the spin coating time is 20 seconds; then, soft baking for 90 seconds to enable the positive photoresist to become a solid film and be attached to the substrate; then, irradiating the substrate with the photoresist by using an exposure machine to transfer the pattern on the photomask to the substrate; finally, the excess photoresist is removed using a diluted developer (EPD48) to form a first blank.

In the magnetron sputtering process, a magnetron radio frequency sputtering system is utilized to sputter a layer of ZnO film with the thickness of 180nm on a photoresist on a blank at room temperature to form a second blank, wherein, as shown in figure 2, the magnetron radio frequency sputtering system comprises a vacuum chamber, a rotating table is arranged in the vacuum chamber, the blank can be placed on the rotating table and can rotate along with the rotating table, a target assembly is arranged above the rotating table, a ZnO target is arranged on the target assembly, a radio frequency instrument can provide RF energy for the target assembly, the upper part of the vacuum chamber is also communicated with an Ar gas cylinder through a pipeline channel, and a flow control valve is also arranged on the pipeline channel.

And in the photoresist removing process, placing the second blank into acetone for standing, after the color of the photoresist of the second blank disappears completely and becomes a transparent ZnO film, cleaning by using DI water, and blow-drying by using a nitrogen gun to form a third blank.

In the hydrothermal synthesis process, the third blank is placed into a hydrothermal reaction pressure kettle, and 20ml of 20% hexamethylene tetramine and 20ml of 20% zinc acetate dihydrate are poured. Reacting at 95 ℃ for 5.5 hours, and then naturally cooling to form the zinc oxide nano-column.

The light measurement system comprises a measurement aluminum box, a measurement base is arranged in the measurement aluminum box, a light-transmitting window is arranged at the upper part of the measurement aluminum box, a UV/LED light source can irradiate the measurement base through the light-transmitting window, and the light measurement system further comprises a measurement ammeter which is connected with a computer. The UV wavelength is 365nm, and the wavelengths of the LED lamp lights with four colors are respectively as follows: 460nm (blue), 540nm (green), 592nm (orange), 630nm (red).

When the light measuring device of the gas sensing element is used, the zinc oxide nano column is placed on the circuit board, the zinc oxide nano column is connected with the upper electrode through the conductive silver adhesive, the connected circuit board is fixed on the measuring base, the connected circuit board is connected to the ammeter in a circuit mode, the distance between the zinc oxide nano column on the circuit board and the light source is 1.3cm, and the measuring aluminum box is in a closed state during light measuring.

The gas sensing element comprises a zinc oxide nano column, the zinc oxide nano column is prepared by the process, a gas measuring device comprises a measuring cavity, a measuring base is arranged in the measuring cavity, the measuring cavity is respectively connected with an air steel cylinder and a gas steel cylinder to be measured through a measuring pipeline, a flow control valve is further arranged on the measuring pipeline, the gas measuring device further comprises a measuring ammeter, the measuring ammeter is connected with a computer, the gas measuring device further comprises a UV light source frame, the UV light source frame is arranged outside a transparent glass cover and fixed through a support, the measuring cavity is composed of the transparent glass cover, and the diameter of the transparent glass cover is about 13 cm.

The use method of the gas measuring device of the gas sensing element is as follows: the method comprises the steps of placing a zinc oxide nano column on a circuit board, connecting the zinc oxide nano column with an upper electrode by using conductive silver adhesive, fixing the connected circuit board in the center of a measuring base, connecting a circuit of the circuit board to an ammeter, arranging the measuring base in the center of a transparent glass cover, controlling respective flow of an air steel cylinder and a gas steel cylinder to be measured by a flow control valve so as to calculate gas concentration, and converging the gas steel cylinder and the gas steel cylinder into the same pipeline to flow into the transparent glass cover.

Next, the zinc oxide nanorods prepared in the present invention were irradiated with UV = light (365nm) and LED light sources of four colors: blue light (460nm), green light (540nm), orange light (592nm), red light (630nm), the results are as follows.

In contrast, the resistance value of the zinc oxide nanopillar is reduced from 18.6M Ω to 615k Ω after being irradiated with UV light, but the nanopillar is not annealed but prepared at a relatively low temperature for a long time by a hydrothermal method lasting 5.5 hours at 95 ℃.

Under the blue LED light, the resistance value is reduced from 19.2M omega to 9.24M omega, under the green LED light, the resistance value is reduced from 18.3M omega to 16.5M omega, and under the irradiation of the orange LED and the red LED, the resistance value is hardly changed. The zinc oxide nano-column prepared by a hydrothermal method hardly has a middle energy gap, so that no light response is generated to orange light LEDs and red light LEDs.

Next, the reaction of the produced zinc oxide nanorods to a gas will be measured in the absence of UV light and in the presence of UV light, and the results are as follows.

The zinc oxide nano-column is measured under the condition of no UV light at normal temperature, and 4000ppm of H is introduced into the zinc oxide nano-column from 180 seconds to 360 seconds₂After that, the resistance value was not significantly changed.

The zinc oxide nanopillars, measured at room temperature without UV light, gradually decreased in resistance after 200 seconds of 500ppm CH4, and returned to the starting point fairly slowly after 400 seconds of gas shut-off.

The zinc oxide nano-column is measured under the condition of UV light at normal temperature, and after 4000ppm of H2 is introduced for 550 seconds to 720 seconds, 920 seconds to 1120 seconds and 1310 seconds to 1500 seconds, the resistance value is slightly reduced and gradually saturated, and the original resistance value can be gradually recovered after the gas is closed.

The zinc oxide nano-column is measured under the condition of UV light at normal temperature, and after 500ppm of CH4 is introduced for 110 seconds to 410 seconds, 850 seconds to 1250 seconds, 1650 seconds to 2050 seconds, the resistance value is greatly reduced and gradually saturated, and the resistance value can be recovered to the original resistance after the gas is closed. In addition, the resistance values recovered after the gas was turned off in the case of irradiation with UV light are not very similar, and it is presumed that gas such as moisture is easily adsorbed to the surface of the sample in the case of irradiation with UV light.

The zinc oxide nano-column is measured under the condition of UV light at normal temperature, and the resistance value is reduced and gradually saturated after 300ppm of CH4 is introduced into the zinc oxide nano-column for 100 seconds to 300 seconds, 520 seconds to 710 seconds and 910 seconds to 1100 seconds. At the same resistance scale, the response was smaller than that of CH4 passing 500 ppm.

The zinc oxide nano-column was measured in the presence of UV light at room temperature, and the resistance value decreased and gradually saturated after CH4 was introduced for about 100 seconds to 300 seconds, 510 seconds to 660 seconds, and 960 seconds to 1120 seconds. At the same resistance scale, the response can be seen to be smaller than with 500ppm and 300ppm CH 4.

The zinc oxide nano-column successfully prepared by the method is arranged on the PET substrate, and the fracture deformation of the PET substrate cannot be caused. Compared with a zinc oxide film which grows on a PET substrate and does not undergo annealing, the zinc oxide nano-column prepared by a hydrothermal method at 95 ℃ for 5.5 hours has quite stable resistance value measured at normal temperature.

The zinc oxide nano-column has a photoresponse value of 312 to UV light, does not react to orange light and red light, and has few energy gaps in zinc oxide prepared by a long-time hydrothermal method. The zinc oxide nano-column is used for measuring CH4 gas at normal temperature, can measure CH4 gas with the concentration as low as 100ppm by matching with the irradiation of UV light at normal temperature, and has positive correlation with the CH4 gas concentration in gas response.

Finally, it should be noted that: the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and a person of ordinary skill in the art can make modifications or equivalents to the specific embodiments of the present invention with reference to the above embodiments, and such modifications or equivalents without departing from the spirit and scope of the present invention are within the scope of the claims of the present invention as set forth in the claims.