WO2024012393A1 - Device for simulating calcium ion dissolution and chloride ion diffusion conditions of cement-based material in underwater area - Google Patents

Device for simulating calcium ion dissolution and chloride ion diffusion conditions of cement-based material in underwater area Download PDF

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Publication number
WO2024012393A1
WO2024012393A1 PCT/CN2023/106510 CN2023106510W WO2024012393A1 WO 2024012393 A1 WO2024012393 A1 WO 2024012393A1 CN 2023106510 W CN2023106510 W CN 2023106510W WO 2024012393 A1 WO2024012393 A1 WO 2024012393A1
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pressure
calcium ion
cement
chloride ion
sensor
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PCT/CN2023/106510
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French (fr)
Chinese (zh)
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金鸣
李文伟
刘加平
曾浩宇
陆超
石妍
张健
杨果
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东南大学
中国长江三峡集团有限公司
长江水利委员会长江科学院
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Publication of WO2024012393A1 publication Critical patent/WO2024012393A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement

Definitions

  • the invention relates to a device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas.
  • the main body of water conservancy projects such as dams is concrete buildings.
  • the concrete buildings below the water level have been in contact with water for a long time.
  • Calcium ions inside the concrete will migrate to the outside driven by the concentration difference. This is called concrete contact corrosion.
  • Contact corrosion of concrete causes decalcification of concrete, which not only reduces the cementing performance of hydrated calcium silicate gel, but also coarsens the porosity of the cementing slurry, leading to continued degradation of the mechanical properties of concrete.
  • the intrusion of chloride ions into the concrete will cause the steel bars to rust, expand and crack, which will lead to a decrease in the bearing capacity of the concrete structure. There is also the danger of calcium ion dissolution.
  • the present invention aims to provide a device that can accurately evaluate the anti-dissolution and anti-erosion properties of cement-based materials in underwater areas of dams and deep-sea projects under the action of different water head pressures by regulating water pressure.
  • the device of the present invention for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas includes a test chamber and an air compressor used to provide pressure for the test chamber; the test chamber includes a resistant
  • the pressure silo and the solution storage silo are equipped with a booster pump and a pressure sensor on the connecting air pipe between the air compressor and the pressure-resistant silo; a sensor assembly is installed in the pressure-resistant silo, and the sensor assembly is fixed on the pressure-resistant silo through a fixing device;
  • the sensor component includes a calcium ion sensor, a chloride ion sensor and a reference electrode; a pressure relief valve is provided on the connecting pipe between the pressure chamber and the solution storage chamber.
  • the booster pump, pressure sensor, calcium ion sensor, chloride ion sensor and pressure relief valve are respectively connected to the PLC control box through cables.
  • the PLC control box communicates with the control terminal with a display screen through a communication module. Interaction.
  • the pressure-resistant chamber is filled with an erosion solution, and the erosion solution is ammonium chloride and/or sodium chloride solution.
  • the concentration of ammonium ions is 0 ⁇ 6mol/L
  • the concentration of chloride ions is 0 ⁇ 9mol/L. L.
  • a cement concrete specimen is placed in the pressure-resistant warehouse, and the powder extraction method of the specimen is to extract powder layer by layer from the exposed surface inwards, with a thickness of 0.5 to 2 mm, preferably 1 mm, for each layer; the obtained powder is ground finely
  • an X-ray fluorescence spectrometer was used to measure the calcium ion content in the powder, and a solid-liquid extraction method combined with a chemical titration method was used to measure the chloride ion content in the powder.
  • the calcium ion dissolution rate and chloride ion content were calculated with the help of the diffusion-dissolution equation of cement-based materials. erosion rate.
  • the calcium ion sensor, chloride ion sensor and reference electrode are flange-mounted on the top cover of the pressure chamber;
  • the measurement range of the calcium ion sensor for the calcium ion concentration in the solution is 10 -5 -10 -1 mol/L , temperature range 5 ⁇ 55°C, diameter 10 ⁇ 15mm, length 100 ⁇ 120mm;
  • the measuring range of chloride ion sensor for chloride ion concentration in solution is 5 ⁇ 10 -5 -10 -1 mol/L, temperature range 5 ⁇ 55°C, diameter 10 ⁇ 1mm, length 100 ⁇ 120mm;
  • the reference electrode is a manganese dioxide solid reference electrode, the temperature range is 5 ⁇ 55°C, the diameter is 5 ⁇ 10mm, and the length is 50 ⁇ 100mm.
  • the calcium ion concentration and chloride ion concentration in the erosion solution are measured in real time through the calcium ion sensor and the chloride ion sensor.
  • the calcium ion concentration or chloride ion concentration in the erosion solution reaches equilibrium (the criterion for reaching balance is: calcium ions and/or chloride ions within one day) If the chloride ion concentration changes no more than 0.5%), update the corrosion solution in the pressure chamber.
  • the pressure-resistant chamber is a plexiglass or stainless steel pressure-resistant chamber; before pouring the corrosion solution into the pressure-resistant chamber, cement-based material specimens are first stably placed in the pressure-resistant chamber, and the total volume of the specimens placed does not exceed the pressure-resistant chamber. 50% of the liquid volume.
  • the solution storage bin is made of organic glass
  • the connecting pipes and the pipes connecting the air pipes are made of stainless steel corrugated explosion-proof braided pipes.
  • the cement-based material specimen is first stably placed in the pressure-resistant chamber, and the total volume of the placed specimen does not exceed 50% of the volume of the pressure-resistant chamber.
  • the device of the present invention can simulate the water head pressure faced by cement-based materials in the underwater area of dams or deep-sea projects. Under the action of water pressure, calcium ions and chloride ions dissolve simultaneously in cement-based materials.
  • the device of the invention can simulate the service environment of concrete at different depths in fresh water or seawater environments, and realize calcium ion dissolution and chloride ion dissolution of cement-based materials under the action of water head pressure Intrusion is carried out simultaneously to evaluate the calcium ion dissolution and chloride ion erosion resistance of cement-based materials under water head pressure conditions and predict their durability.
  • Figure 1 is a schematic structural diagram of the device of the present invention.
  • the device of the present invention for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas includes a test chamber and an air compressor used to provide pressure for the test chamber; the test chamber includes a pressure-resistant chamber and solution storage warehouse.
  • the connecting air pipe between the air compressor and the pressure-resistant warehouse is equipped with a booster pump and a pressure sensor; a calcium ion sensor and a chloride ion sensor are installed in the pressure-resistant warehouse; and the connecting pipe between the pressure-resistant warehouse and the solution storage warehouse is equipped with a booster pump and a pressure sensor.
  • the booster pump is a liquid booster pump.
  • the air compressor provides gas pressure to the booster pump.
  • the booster pump drives the gas to pressurize the corrosive liquid.
  • the hydraulic sensor and the pressure relief valve work together to accurately control the corrosive liquid in the cylindrical pressure chamber.
  • the solution storage bin is used to store etching solutions.
  • the device of the present invention also includes a PLC control box (data receiving device).
  • the booster pump, pressure sensor, calcium ion sensor, chloride ion sensor and pressure relief valve are respectively connected to the PLC control box through cables.
  • the PLC control box is connected to the PLC control box through a communication module. Control terminal with display screen for information exchange.
  • the device of the invention monitors the concentration of calcium ions and chloride ions in the erosion solution in real time through a calcium ion sensor and a chloride ion sensor.
  • the pressure-resistant warehouse is a cylindrical pressure-resistant warehouse with a diameter of 10-50cm, preferably 30cm; a height of 10-120cm, preferably 80cm; the pressure-resistant warehouse can withstand a pressure range of 0-5MPa; the material used is organic glass or stainless steel, preferably transparent Plexiglas, yes
  • the pressure-resistant chamber made of plexiglass will not corrode, and the test conditions in the pressure-resistant chamber can be observed in real time. Before pouring the corrosion solution into the pressure chamber, the cement-based material specimen shall be stably placed in the pressure chamber, and the total volume of the specimen placed shall not exceed 50% of the volume of the pressure chamber.
  • the pressure-resistant chamber is filled with an erosion solution, and the erosion solution is ammonium chloride and/or sodium chloride solution.
  • the concentration of ammonium ions is 0 to 6 mol/L
  • the concentration of chloride ions is 0 to 9 mol/L.
  • the present invention can simultaneously obtain the results of the diffusion of chloride ions from the external solution to the interior of the cement-based material under pressurized conditions by adjusting the concentration and components of the erosion solution (ammonium chloride solution). The result of the diffusion of chloride ions from the external solution into the interior of the cement-based material and the diffusion of calcium ions from the cement-based material into the external solution under the conditions.
  • a cement concrete specimen is placed in the pressure chamber.
  • the method of extracting powder from the specimen is to extract powder layer by layer from the exposed surface inward.
  • the thickness of each layer is 0.5 to 2 mm, preferably 1 mm; after grinding the obtained powder, An X-ray fluorescence spectrometer was used to measure the calcium ion content in the powder.
  • the solid-liquid extraction method combined with the chemical titration method was used to measure the chloride ion content in the powder.
  • the sample was layered to take powder to measure the calcium ions and calcium ions in the cement slurry. For chloride ion content, the calcium ion dissolution rate and chloride ion diffusion rate are calculated based on the cement-based material diffusion-dissolution equation.
  • the pressure-resistant solid-state calcium ion sensor, chloride ion sensor and reference electrode are flange-mounted on the top cover of the pressure-resistant chamber;
  • the measurement range of the calcium ion sensor for the calcium ion concentration in the solution is 10 -5 -10 -1 mol/ L, temperature range 5 ⁇ 55°C, diameter 10 ⁇ 15mm, length 100 ⁇ 120mm;
  • the chloride ion sensor's measurement range of chloride ion concentration in the solution is 5 ⁇ 10 -5 -10 -1 mol/L, temperature range 5 ⁇ 55 °C, diameter 10 ⁇ 1mm, length 100 ⁇ 120mm;
  • the reference electrode is manganese dioxide solid reference electrode, temperature range 5 ⁇ 55°C, diameter 5 ⁇ 10mm, length 50 ⁇ 100mm.
  • the calcium ion concentration and chloride ion concentration in the erosion solution are monitored in real time through the calcium ion sensor and the chloride ion sensor. When the calcium ion concentration or chloride ion concentration in the erosion solution reaches equilibrium, the erosion solution in the pressure chamber is updated.
  • the solution storage bin has a diameter of 50cm and a height of 120cm, and is made of plexiglass;
  • the connecting pipe and the pipe connecting the air pipe are made of stainless steel corrugated explosion-proof braided pipe, with a maximum working pressure of 20MPa, and the maximum working pressure of the pipeline is far beyond the capabilities of the equipment.
  • the maximum pressure applied ensures the safety of the pipeline during the test; in addition, the stainless steel material will not react with acidic solutions and has good durability.
  • the core component of the hydraulic sensor is 316L stainless steel, with a range of -0.1 ⁇ 50MPa and a resolution of 0.1MPa; the measurement accuracy is ⁇ 0.1% of the full scale, the overload capacity is 200% of the full scale, and the temperature drift coefficient is ⁇ 0.05% of the full scale/°C.
  • the pressure chamber is controlled by the hydraulic sensor to achieve and maintain the set pressure.
  • the core component of the pressure relief valve is 316L stainless steel, with an operating pressure of 0.05 ⁇ 10MPa.
  • the pressure relief will be automatically opened to ensure the pressure of the corrosive medium (erosive solution) in the equipment and pipelines. Under the set pressure, prevent accidents.
  • the device of the invention can accurately control the pressure applied to the erosion solution to simulate the head pressure endured by concrete buildings at different water depths; in addition, the compound solution of ammonium chloride and calcium chloride can be used to simulate the pressure faced by the concrete structure.
  • Different environments of simple calcium ion dissolution and coupling of calcium ion dissolution and chloride ion erosion By measuring the calcium ion dissolution rate and chloride ion erosion rate of cement-based materials under different pressures, the corrosion resistance and corrosion resistance of cement-based materials under different water head pressures can be measured. Accurate evaluation of corrosion resistance.
  • the diameter of the slurry specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98 ⁇ 2%, temperature 20 ⁇ 1°C) for 28 days.
  • the side of the cured cement slurry specimen is sealed with epoxy resin, and the apparatus of the present invention is used to conduct calcium ion dissolution and chloride ion diffusion tests under corresponding water pressure of the specimen.
  • the dissolution medium is 1 mol/L ammonium chloride solution.
  • the applied pressures are 0, 0.5, 1.0, 1.5, and 2.0MPa respectively.
  • the erosion times are set to 28, 56, 97, and 140d respectively. The clean slurry is tested at each dissolution time.
  • the diameter of the concrete specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98 ⁇ 2%, temperature 20 ⁇ 1°C) for 28 days.
  • the side of the cured concrete specimen is sealed with epoxy resin, and the device of the present invention is used to conduct calcium ion dissolution and chloride ion diffusion tests under water pressure.
  • the dissolution medium is 1 mol/L ammonium chloride solution.
  • the applied pressures are 0, 0.5, 1.0, 1.5, and 2.0MPa respectively.
  • the erosion times are set to 28, 56, 97, and 140 days respectively.
  • the concrete specimens are taken out at each corrosion time.
  • the diameter of the concrete specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98 ⁇ 2%, temperature 20 ⁇ 1°C) for 28 days.
  • the side of the cured concrete specimen is sealed with epoxy resin, and the device of the present invention is used to conduct calcium ion dissolution and chloride ion diffusion tests under water pressure.
  • the dissolution medium is ammonium chloride solution of 0.1, 0.5, 1, 3, and 5 mol/L.
  • the trial pressure is 0MPa.
  • the erosion time is set to 28, 56, 97, and 140d respectively. At each dissolution time, the concrete specimens are taken out and analyzed.
  • the diameter of the concrete specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98 ⁇ 2%, temperature 20 ⁇ 1°C) for 28 days.
  • the sides of the cured concrete specimens are sealed with epoxy resin, and the device of the invention is used to conduct concrete freshwater dissolution and seawater dissolution and erosion tests under water pressure.
  • the corrosion media were tap water (simulated fresh water) and 3.5% sodium chloride solution (simulated seawater).
  • the trial pressures were 0 and 1.0MPa respectively.
  • the erosion times were set to 28, 56, 97, and 140 days respectively.
  • the present invention simulates the head load faced by the cement-based materials in the underwater area by pressurizing the solution to achieve the synergistic effect of the water head pressure, calcium ion dissolution and chloride ion erosion, and can more accurately reflect the cement-based materials in the underwater area under the action of water head pressure. Calcium ion dissolution rate and chloride ion erosion rate can more accurately evaluate the anti-dissolution and anti-erosion properties of cement-based materials under the action of water head pressure.

Abstract

A device for simulating calcium ion dissolution and chloride ion diffusion conditions of a cement-based material in an underwater area, said device comprising a test bin and an air compressor for providing pressure for the test bin; the test bin comprises a pressure-resistant bin and a solution storage bin, and a booster pump and a pressure sensor are arranged on a connecting air pipe of the air compressor and the pressure-resistant bin; a sensor assembly is disposed in the pressure-resistant bin, and the sensor assembly is fixed to the pressure-resistant bin by means of a fixing device; the sensor assembly comprises a calcium ion sensor, a chloride ion sensor and a reference electrode; and a pressure relief valve is disposed on a connecting pipe of the pressure-resistant bin and the solution storage bin. In the device, pressure is applied to a corrosive solution to simulate the head pressure acting on a cement-based material in an underwater area of a dam or deep-sea engineering. Under the action of water pressure, the cement-based material experiences calcium ion dissolution and chloride ion erosion at the same time, so that the calcium ion dissolution rate and the chloride ion diffusion rate of the cement-based material under the action of corresponding water pressure are rapidly obtained. The corrosion resistance and chloride ion erosion resistance of the cement-based material under the action of different water pressures may be evaluated, and the service life of a concrete building under the conditions of water pressure load and during calcium ion dissolution and chloride ion erosion degradation may be predicted.

Description

一种用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置A device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas 技术领域Technical field
本发明涉及一种用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置。The invention relates to a device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas.
背景技术Background technique
大坝等水利工程主体为混凝土建筑物，水位下方的混凝土建筑物长期与水接触，混凝土内部钙离子会在浓度差的驱动下向外部迁移，以上被称为混凝土接触溶蚀。混凝土接触溶蚀造成混凝土脱钙，不仅降低水化硅酸钙凝胶的胶结性能，而且粗化胶结浆体的孔隙率，导致混凝土力学性能的持续退化。另外，对于深海混凝土工程，由于海水中氯离子含量较高，氯离子侵入混凝土会造成钢筋锈胀开裂进而导致混凝土结构承载力下降，同时也存在钙离子溶出的危害。The main body of water conservancy projects such as dams is concrete buildings. The concrete buildings below the water level have been in contact with water for a long time. Calcium ions inside the concrete will migrate to the outside driven by the concentration difference. This is called concrete contact corrosion. Contact corrosion of concrete causes decalcification of concrete, which not only reduces the cementing performance of hydrated calcium silicate gel, but also coarsens the porosity of the cementing slurry, leading to continued degradation of the mechanical properties of concrete. In addition, for deep-sea concrete projects, due to the high chloride ion content in seawater, the intrusion of chloride ions into the concrete will cause the steel bars to rust, expand and crack, which will lead to a decrease in the bearing capacity of the concrete structure. There is also the danger of calcium ion dissolution.
目前关于水泥基材料溶蚀劣化和氯离子侵蚀的研究主要针对常压条件，但是无论是大坝还是深海建筑其水下区混凝土均受到水头荷载作用，并且水头压力随着水位深度的增加而增大。很多水电站蓄水深度和深海混凝土建造深度均超过100米，底部混凝土受到的压强更是超过了1MPa的水头压力。相较于常压条件，水头压力使溶蚀介质能够更轻易地侵入到混凝土内部更深的位置，也促进更深位置处水泥浆体中的钙离子扩散到混凝土外部。Current research on the corrosion deterioration and chloride ion erosion of cement-based materials is mainly focused on normal pressure conditions. However, whether it is a dam or a deep-sea building, the concrete in the underwater area is subject to water head load, and the head pressure increases with the increase of water level depth. . The water storage depth of many hydropower stations and the construction depth of deep-sea concrete exceed 100 meters, and the pressure on the bottom concrete exceeds the head pressure of 1MPa. Compared with normal pressure conditions, water head pressure allows the corrosive medium to invade deeper inside the concrete more easily, and also promotes the diffusion of calcium ions in the cement paste at deeper locations to the outside of the concrete.
发明内容Contents of the invention
发明目的：本发明旨在提供一种能够通过调控水压力从而能够准确评估出在不同水头压力作用下大坝和深海工程水下区水泥基材料的抗溶蚀和抗侵蚀性能的装置。Purpose of the invention: The present invention aims to provide a device that can accurately evaluate the anti-dissolution and anti-erosion properties of cement-based materials in underwater areas of dams and deep-sea projects under the action of different water head pressures by regulating water pressure.
技术方案：本发明所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，包括试验仓以及用于为试验仓提供压力的空气压缩机；所述试验仓包括耐压仓和溶液存储仓，空气压缩机与耐压仓的连接气管上设有增压泵和压力传感器；在耐压仓内装有传感器组件，传感器组件通过固定装置固定在耐压仓上；所述传感器组件包括钙离子传感器、氯离子传感器和参比电极；在耐压仓和溶液存储仓的连接管道上设有泄压阀。Technical solution: The device of the present invention for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas includes a test chamber and an air compressor used to provide pressure for the test chamber; the test chamber includes a resistant The pressure silo and the solution storage silo are equipped with a booster pump and a pressure sensor on the connecting air pipe between the air compressor and the pressure-resistant silo; a sensor assembly is installed in the pressure-resistant silo, and the sensor assembly is fixed on the pressure-resistant silo through a fixing device; The sensor component includes a calcium ion sensor, a chloride ion sensor and a reference electrode; a pressure relief valve is provided on the connecting pipe between the pressure chamber and the solution storage chamber.
其中，还包括PLC控制箱，增压泵、压力传感器、钙离子传感器、氯离子传感器和泄压阀分别通过电缆与PLC控制箱连接，PLC控制箱通过通讯模块与带显示屏的控制终端进行信息交互。It also includes a PLC control box. The booster pump, pressure sensor, calcium ion sensor, chloride ion sensor and pressure relief valve are respectively connected to the PLC control box through cables. The PLC control box communicates with the control terminal with a display screen through a communication module. Interaction.
其中，所述耐压仓内填充有侵蚀溶液，侵蚀溶液为氯化铵和/或氯化钠溶液，溶液中，铵根离子的浓度为0～6mol/L，氯离子浓度为0～9mol/L。Wherein, the pressure-resistant chamber is filled with an erosion solution, and the erosion solution is ammonium chloride and/or sodium chloride solution. In the solution, the concentration of ammonium ions is 0~6mol/L, and the concentration of chloride ions is 0~9mol/L. L.
其中，所述耐压仓内放置有水泥混凝土试件，所述试件取粉方式为由暴露面向内逐层取粉，每层取粉厚度0.5～2mm，优选1mm；对取得的粉磨细后，使用X射线荧光光谱仪测定粉末中钙离子含量，同时用固液萃取法结合化学滴定法测定粉末中氯离子含量，借助于水泥基材料的扩散-溶解方程计算出钙离子溶出速率和氯离子侵蚀速率。Wherein, a cement concrete specimen is placed in the pressure-resistant warehouse, and the powder extraction method of the specimen is to extract powder layer by layer from the exposed surface inwards, with a thickness of 0.5 to 2 mm, preferably 1 mm, for each layer; the obtained powder is ground finely Finally, an X-ray fluorescence spectrometer was used to measure the calcium ion content in the powder, and a solid-liquid extraction method combined with a chemical titration method was used to measure the chloride ion content in the powder. The calcium ion dissolution rate and chloride ion content were calculated with the help of the diffusion-dissolution equation of cement-based materials. erosion rate.
其中，所述钙离子传感器、氯离子传感器和参比电极用法兰方式安装在耐压仓顶部盖板上；钙离子传感器对溶液中钙离子浓度的测量范围10-5-10-1mol/L，温度范围5～55℃，直径 10～15mm，长度100～120mm；氯离子传感器对溶液中氯离子浓度的测量范围为5×10-5-10-1mol/L，温度范围5～55℃，直径10～1mm，长度100～120mm；参比电极为二氧化锰固体参比电极，温度范围5～55℃，直径5～10mm，长度50～100mm。通过钙离子传感器和氯离子传感器实时掌握侵蚀溶液中钙离子浓度和氯离子浓度，当侵蚀溶液中钙离子浓度或氯离子浓度达到平衡时(达到平衡的判断标准为：一天内钙离子和/或氯离子浓度变化不超过0.5％)，则更新耐压仓中的侵蚀溶液。Among them, the calcium ion sensor, chloride ion sensor and reference electrode are flange-mounted on the top cover of the pressure chamber; the measurement range of the calcium ion sensor for the calcium ion concentration in the solution is 10 -5 -10 -1 mol/L , temperature range 5～55℃, diameter 10～15mm, length 100～120mm; the measuring range of chloride ion sensor for chloride ion concentration in solution is 5×10 -5 -10 -1 mol/L, temperature range 5～55℃, diameter 10～1mm, length 100～ 120mm; the reference electrode is a manganese dioxide solid reference electrode, the temperature range is 5~55℃, the diameter is 5~10mm, and the length is 50~100mm. The calcium ion concentration and chloride ion concentration in the erosion solution are measured in real time through the calcium ion sensor and the chloride ion sensor. When the calcium ion concentration or chloride ion concentration in the erosion solution reaches equilibrium (the criterion for reaching balance is: calcium ions and/or chloride ions within one day) If the chloride ion concentration changes no more than 0.5%), update the corrosion solution in the pressure chamber.
其中，所述耐压仓为有机玻璃或不锈钢耐压仓；向耐压仓灌注侵蚀溶液前，先将水泥基材料试件稳定放置于耐压仓内，所放入试件总体积不超过耐压仓体积的50％。Wherein, the pressure-resistant chamber is a plexiglass or stainless steel pressure-resistant chamber; before pouring the corrosion solution into the pressure-resistant chamber, cement-based material specimens are first stably placed in the pressure-resistant chamber, and the total volume of the specimens placed does not exceed the pressure-resistant chamber. 50% of the liquid volume.
其中，溶液存储仓为有机玻璃制备而成，连接管道和连接气管的管路材质均为不锈钢波纹防爆编织管。Among them, the solution storage bin is made of organic glass, and the connecting pipes and the pipes connecting the air pipes are made of stainless steel corrugated explosion-proof braided pipes.
其中，所述的向耐压仓灌注溶液前，先将水泥基材料试件稳定放置于耐压仓内，所放入的试件总体积不超过耐压仓体积的50％。Wherein, before pouring the solution into the pressure-resistant chamber, the cement-based material specimen is first stably placed in the pressure-resistant chamber, and the total volume of the placed specimen does not exceed 50% of the volume of the pressure-resistant chamber.
有益效果：本发明装置通过对侵蚀溶液施加压强，可以模拟出大坝或深海工程水下区水泥基材料面临的水头压力作用，在水压力作用下，水泥基材料同时发生钙离子溶出与氯离子侵蚀，从而快速得到在对应水压力作用下水泥基材料的钙离子溶出速率与氯离子扩散速率，评价不同水压力作用下水泥基材料的抗溶蚀和抗氯离子侵蚀性能，预测出水压力荷载条件下遭受钙离子溶出与氯离子侵蚀劣化时混凝土建筑物的服役寿命；本发明装置能够模拟淡水或海水环境中不同深度位置处混凝土的服役环境，实现水头压力作用下水泥基材料钙离子溶出与氯离子侵入的同时进行，评价水头压力条件下水泥基材料的抗钙离子溶出和抗氯离子侵蚀性能并预测其耐久性。Beneficial effects: By applying pressure to the erosion solution, the device of the present invention can simulate the water head pressure faced by cement-based materials in the underwater area of dams or deep-sea projects. Under the action of water pressure, calcium ions and chloride ions dissolve simultaneously in cement-based materials. Erosion, thereby quickly obtaining the calcium ion dissolution rate and chloride ion diffusion rate of cement-based materials under the corresponding water pressure, evaluating the corrosion resistance and chloride ion erosion resistance of cement-based materials under different water pressures, and predicting the conditions under water pressure load The service life of concrete buildings when subjected to calcium ion dissolution and chloride ion erosion and deterioration; the device of the invention can simulate the service environment of concrete at different depths in fresh water or seawater environments, and realize calcium ion dissolution and chloride ion dissolution of cement-based materials under the action of water head pressure Intrusion is carried out simultaneously to evaluate the calcium ion dissolution and chloride ion erosion resistance of cement-based materials under water head pressure conditions and predict their durability.
附图说明Description of drawings
图1为本发明装置的结构原理图。Figure 1 is a schematic structural diagram of the device of the present invention.
具体实施方式Detailed ways
如图1所示，本发明用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，包括试验仓以及用于为试验仓提供压力的空气压缩机；试验仓包括耐压仓和溶液存储仓，空气压缩机与耐压仓的连接气管上设有增压泵和压力传感器；在耐压仓内装有钙离子传感器和氯离子传感器；在耐压仓和溶液存储仓的连接管道上设有泄压阀。增压泵为液体增压泵，空气压缩机向增压泵提供气体压力，增压泵驱动气体对溶蚀液体增压，液压传感器和泄压阀协同工作精确控制对圆柱形耐压仓内溶蚀液体所施加的压强。溶液存储仓用于存放侵蚀溶液。As shown in Figure 1, the device of the present invention for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas includes a test chamber and an air compressor used to provide pressure for the test chamber; the test chamber includes a pressure-resistant chamber and solution storage warehouse. The connecting air pipe between the air compressor and the pressure-resistant warehouse is equipped with a booster pump and a pressure sensor; a calcium ion sensor and a chloride ion sensor are installed in the pressure-resistant warehouse; and the connecting pipe between the pressure-resistant warehouse and the solution storage warehouse is equipped with a booster pump and a pressure sensor. There is a pressure relief valve on it. The booster pump is a liquid booster pump. The air compressor provides gas pressure to the booster pump. The booster pump drives the gas to pressurize the corrosive liquid. The hydraulic sensor and the pressure relief valve work together to accurately control the corrosive liquid in the cylindrical pressure chamber. The pressure applied. The solution storage bin is used to store etching solutions.
其中，本发明装置还包括PLC控制箱(数据接收装置)，增压泵、压力传感器、钙离子传感器、氯离子传感器和泄压阀分别通过电缆与PLC控制箱连接，PLC控制箱通过通讯模块与带显示屏的控制终端进行信息交互。本发明装置通过钙离子传感器和氯离子传感器实时监测侵蚀溶液中的钙离子和氯离子浓度。Among them, the device of the present invention also includes a PLC control box (data receiving device). The booster pump, pressure sensor, calcium ion sensor, chloride ion sensor and pressure relief valve are respectively connected to the PLC control box through cables. The PLC control box is connected to the PLC control box through a communication module. Control terminal with display screen for information exchange. The device of the invention monitors the concentration of calcium ions and chloride ions in the erosion solution in real time through a calcium ion sensor and a chloride ion sensor.
耐压仓为圆柱形耐压仓，直径为10～50cm，优选30cm；高度为10～120cm，优选80cm；耐压仓所能承受压强范围0～5MPa；所用材质为有机玻璃或不锈钢，优选透明有机玻璃，有 机玻璃材质制备的耐压仓既不发生腐蚀，还能实时观察耐压仓内的试验情况。向耐压仓灌注侵蚀溶液前，先将水泥基材料试件稳定放置于耐压仓内，所放入试件总体积不超过耐压仓体积的50％。The pressure-resistant warehouse is a cylindrical pressure-resistant warehouse with a diameter of 10-50cm, preferably 30cm; a height of 10-120cm, preferably 80cm; the pressure-resistant warehouse can withstand a pressure range of 0-5MPa; the material used is organic glass or stainless steel, preferably transparent Plexiglas, yes The pressure-resistant chamber made of plexiglass will not corrode, and the test conditions in the pressure-resistant chamber can be observed in real time. Before pouring the corrosion solution into the pressure chamber, the cement-based material specimen shall be stably placed in the pressure chamber, and the total volume of the specimen placed shall not exceed 50% of the volume of the pressure chamber.
其中，耐压仓内填充有侵蚀溶液，侵蚀溶液为氯化铵和/或氯化钠溶液，溶液中，铵根离子的浓度为0～6mol/L，氯离子浓度为0～9mol/L。短时间内只能得到在加压条件下氯离子从外部溶液向水泥基材料内部扩散的结果，而本发明通过侵蚀溶液浓度和组分的调整(氯化铵溶液)，能够同时得到在加压条件下氯离子从外部溶液向水泥基材料内部扩散以及钙离子从水泥基材料扩散到外部溶液的结果。Among them, the pressure-resistant chamber is filled with an erosion solution, and the erosion solution is ammonium chloride and/or sodium chloride solution. In the solution, the concentration of ammonium ions is 0 to 6 mol/L, and the concentration of chloride ions is 0 to 9 mol/L. In a short period of time, only the result of chloride ions diffusing from the external solution to the interior of the cement-based material under pressurized conditions can be obtained. However, the present invention can simultaneously obtain the results of the diffusion of chloride ions from the external solution to the interior of the cement-based material under pressurized conditions by adjusting the concentration and components of the erosion solution (ammonium chloride solution). The result of the diffusion of chloride ions from the external solution into the interior of the cement-based material and the diffusion of calcium ions from the cement-based material into the external solution under the conditions.
其中，耐压仓内放置有水泥混凝土试件，所述试件取粉方式为由暴露面向内逐层取粉，每层取粉厚度0.5～2mm，优选1mm；对取得的粉磨细后，使用X射线荧光光谱仪测定粉末中钙离子含量，同时用固液萃取法结合化学滴定法测定粉末中氯离子含量，在加压侵蚀后对试件分层取粉测定水泥浆体中的钙离子和氯离子含量，根据水泥基材料扩散-溶解方程计算出钙离子溶出速率和氯离子扩散速率。Among them, a cement concrete specimen is placed in the pressure chamber. The method of extracting powder from the specimen is to extract powder layer by layer from the exposed surface inward. The thickness of each layer is 0.5 to 2 mm, preferably 1 mm; after grinding the obtained powder, An X-ray fluorescence spectrometer was used to measure the calcium ion content in the powder. At the same time, the solid-liquid extraction method combined with the chemical titration method was used to measure the chloride ion content in the powder. After pressure erosion, the sample was layered to take powder to measure the calcium ions and calcium ions in the cement slurry. For chloride ion content, the calcium ion dissolution rate and chloride ion diffusion rate are calculated based on the cement-based material diffusion-dissolution equation.
其中，耐压固态钙离子传感器、氯离子传感器和参比电极用法兰方式安装在耐压仓顶部盖板上；钙离子传感器对溶液中钙离子浓度的测量范围10-5-10-1mol/L，温度范围5～55℃，直径10～15mm，长度100～120mm；氯离子传感器对溶液中氯离子浓度的测量范围为5×10-5-10-1mol/L，温度范围5～55℃，直径10～1mm，长度100～120mm；参比电极为二氧化锰固体参比电极，温度范围5～55℃，直径5～10mm，长度50～100mm。通过钙离子传感器和氯离子传感器实时掌握侵蚀溶液中钙离子浓度和氯离子浓度，当侵蚀溶液中钙离子浓度或氯离子浓度达到平衡时，则更新耐压仓中的侵蚀溶液。Among them, the pressure-resistant solid-state calcium ion sensor, chloride ion sensor and reference electrode are flange-mounted on the top cover of the pressure-resistant chamber; the measurement range of the calcium ion sensor for the calcium ion concentration in the solution is 10 -5 -10 -1 mol/ L, temperature range 5~55℃, diameter 10~15mm, length 100~120mm; the chloride ion sensor's measurement range of chloride ion concentration in the solution is 5×10 -5 -10 -1 mol/L, temperature range 5~55 ℃, diameter 10~1mm, length 100~120mm; the reference electrode is manganese dioxide solid reference electrode, temperature range 5~55℃, diameter 5~10mm, length 50~100mm. The calcium ion concentration and chloride ion concentration in the erosion solution are monitored in real time through the calcium ion sensor and the chloride ion sensor. When the calcium ion concentration or chloride ion concentration in the erosion solution reaches equilibrium, the erosion solution in the pressure chamber is updated.
其中，溶液存储仓直径50cm，高度120cm，为有机玻璃制备而成；连接管道和连接气管的管路材质均为不锈钢波纹防爆编织管，最大工作压力20MPa，管路最大工作压力远超设备所能施加的最大压力，确保了试验中管路的安全性；另外不锈钢材质不会与酸性溶液发生反应，具有良好的耐久性。Among them, the solution storage bin has a diameter of 50cm and a height of 120cm, and is made of plexiglass; the connecting pipe and the pipe connecting the air pipe are made of stainless steel corrugated explosion-proof braided pipe, with a maximum working pressure of 20MPa, and the maximum working pressure of the pipeline is far beyond the capabilities of the equipment. The maximum pressure applied ensures the safety of the pipeline during the test; in addition, the stainless steel material will not react with acidic solutions and has good durability.
其中，液压传感器核心部件为316L不锈钢，量程范围-0.1～50MPa,分辨率0.1MPa；测量精度±0.1％满量程，过载能力200％满量程，温度漂移系数±0.05％满量程/℃。设置好试验的压强值后，通过液压传感器调控耐压仓达到并维持所设定的压强。Among them, the core component of the hydraulic sensor is 316L stainless steel, with a range of -0.1~50MPa and a resolution of 0.1MPa; the measurement accuracy is ±0.1% of the full scale, the overload capacity is 200% of the full scale, and the temperature drift coefficient is ±0.05% of the full scale/°C. After setting the test pressure value, the pressure chamber is controlled by the hydraulic sensor to achieve and maintain the set pressure.
其中，泄压阀核心部件为316L不锈钢，使用压力0.05～10MPa，当管路内压力超过泄压阀设定压力时，即自动开启泄压，保证设备和管道内的溶蚀介质(侵蚀溶液)压力在设定压力之下，防止发生意外。Among them, the core component of the pressure relief valve is 316L stainless steel, with an operating pressure of 0.05~10MPa. When the pressure in the pipeline exceeds the set pressure of the pressure relief valve, the pressure relief will be automatically opened to ensure the pressure of the corrosive medium (erosive solution) in the equipment and pipelines. Under the set pressure, prevent accidents.
本发明装置能够精确控制对侵蚀溶液所施加的压强，以模拟不同水位深度时混凝土建筑物所承受的水头压力；另外，采用氯化铵与氯化钙的复配溶液，可以模拟混凝土结构所面临的单纯钙离子溶出以及钙离子溶出与氯离子侵蚀耦合的不同环境，通过测定不同压强下水泥基材料钙离子溶出速率与氯离子侵蚀速率，实现对不同水头压力下水泥基材料的抗溶蚀性能与抗侵蚀性能做出准确评价。 The device of the invention can accurately control the pressure applied to the erosion solution to simulate the head pressure endured by concrete buildings at different water depths; in addition, the compound solution of ammonium chloride and calcium chloride can be used to simulate the pressure faced by the concrete structure. Different environments of simple calcium ion dissolution and coupling of calcium ion dissolution and chloride ion erosion. By measuring the calcium ion dissolution rate and chloride ion erosion rate of cement-based materials under different pressures, the corrosion resistance and corrosion resistance of cement-based materials under different water head pressures can be measured. Accurate evaluation of corrosion resistance.
实施例1Example 1
制备多个水灰比为0.5的圆柱形水泥净浆试件，净浆试件的直径为10cm、高度为5cm，在养护箱(湿度98±2％，温度20±1℃)中养护28d。将养护后的水泥净浆试件侧面用环氧树脂密封，采用本发明装置进行该试件对应水压力下钙离子溶出和氯离子扩散试验。溶蚀介质为1mol/L的氯化铵溶液，施加的压强分别为0、0.5、1.0、1.5、2.0MPa，侵蚀时间分别设置为28、56、97、140d，在每个溶蚀时间取出净浆试件分层取粉测试粉末中的钙离子含量和氯离子含量。140d后不同压强条件下水泥净浆的钙离子溶出速率和氯离子侵蚀速率分别如表1所示，结果表明水泥净浆中钙离子溶出速率和氯离子侵蚀速率均随着水头压力增加而增大。Prepare multiple cylindrical cement slurry specimens with a water-cement ratio of 0.5. The diameter of the slurry specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98±2%, temperature 20±1°C) for 28 days. The side of the cured cement slurry specimen is sealed with epoxy resin, and the apparatus of the present invention is used to conduct calcium ion dissolution and chloride ion diffusion tests under corresponding water pressure of the specimen. The dissolution medium is 1 mol/L ammonium chloride solution. The applied pressures are 0, 0.5, 1.0, 1.5, and 2.0MPa respectively. The erosion times are set to 28, 56, 97, and 140d respectively. The clean slurry is tested at each dissolution time. Take the powder in layers to test the calcium ion content and chloride ion content in the powder. The calcium ion dissolution rate and chloride ion erosion rate of cement paste under different pressure conditions after 140 days are shown in Table 1 respectively. The results show that the calcium ion dissolution rate and chloride ion erosion rate in cement paste increase with the increase of water head pressure. .
表1不同水头压力下水泥净浆钙离子溶出速率和氯离子侵蚀速率
Table 1 Calcium ion dissolution rate and chloride ion erosion rate of cement paste under different water head pressures
实施例2Example 2
制备多个水灰比为0.5的圆柱形混凝土试件，混凝土试件的直径为10cm、高度为5cm，在养护箱(湿度98±2％，温度20±1℃)中养护28d。将养护后的混凝土试件侧面用环氧树脂密封，采用本发明装置进行水压力下钙离子溶出和氯离子扩散试验。溶蚀介质为1mol/L的氯化铵溶液，施加的压强分别为0、0.5、1.0、1.5、2.0MPa，侵蚀时间分别设置为28、56、97、140d，在每个溶蚀时间取出混凝土试件分层取粉测试粉末中的钙离子含量和氯离子含量。140d后不同压强条件下混凝土的钙离子溶出速率和氯离子侵蚀速率分别如表2所示，结果表明水泥混凝土中钙离子溶出速率和氯离子侵蚀速率均随着水头压力增加而增大。Prepare multiple cylindrical concrete specimens with a water-cement ratio of 0.5. The diameter of the concrete specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98±2%, temperature 20±1°C) for 28 days. The side of the cured concrete specimen is sealed with epoxy resin, and the device of the present invention is used to conduct calcium ion dissolution and chloride ion diffusion tests under water pressure. The dissolution medium is 1 mol/L ammonium chloride solution. The applied pressures are 0, 0.5, 1.0, 1.5, and 2.0MPa respectively. The erosion times are set to 28, 56, 97, and 140 days respectively. The concrete specimens are taken out at each corrosion time. Take the powder in layers to test the calcium ion content and chloride ion content in the powder. The calcium ion dissolution rate and chloride ion erosion rate of concrete under different pressure conditions after 140 days are shown in Table 2. The results show that the calcium ion dissolution rate and chloride ion erosion rate in cement concrete increase with the increase of water head pressure.
表2不同水头压力下混凝土钙离子溶出速率和氯离子侵蚀速率
Table 2 Calcium ion dissolution rate and chloride ion erosion rate of concrete under different water head pressures
实施例3Example 3
制备多个水灰比为0.5的圆柱形混凝土试件，混凝土试件的直径为10cm、高度为5cm，在养护箱(湿度98±2％，温度20±1℃)中养护28d。将养护后的混凝土试件侧面用环氧树脂密封，采用本发明装置进行水压力下钙离子溶出和氯离子扩散试验。溶蚀介质为0.1、0.5、1、3、5mol/L的氯化铵溶液，试加的压强为0MPa，侵蚀时间分别设置为28、56、97、140d，在每个溶蚀时间取出混凝土试件分层取粉测试粉末中的钙离子含量和氯离子含量。不同氯化铵浓度条件下混凝土的钙离子溶出速率和氯离子侵蚀速率分别如表3所示，结果表明混凝土中钙离子溶出速率和氯离子侵蚀速率均随着氯化铵浓度增加而增大。Prepare multiple cylindrical concrete specimens with a water-cement ratio of 0.5. The diameter of the concrete specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98±2%, temperature 20±1°C) for 28 days. The side of the cured concrete specimen is sealed with epoxy resin, and the device of the present invention is used to conduct calcium ion dissolution and chloride ion diffusion tests under water pressure. The dissolution medium is ammonium chloride solution of 0.1, 0.5, 1, 3, and 5 mol/L. The trial pressure is 0MPa. The erosion time is set to 28, 56, 97, and 140d respectively. At each dissolution time, the concrete specimens are taken out and analyzed. Take the powder layer by layer to test the calcium ion content and chloride ion content in the powder. The calcium ion dissolution rate and chloride ion erosion rate of concrete under different ammonium chloride concentrations are shown in Table 3. The results show that the calcium ion dissolution rate and chloride ion erosion rate in concrete increase as the ammonium chloride concentration increases.
表3不同氯化铵浓度下混凝土钙离子溶出速率和氯离子侵蚀速率

Table 3 Calcium ion dissolution rate and chloride ion erosion rate of concrete under different ammonium chloride concentrations

实施例4Example 4
制备多个水灰比为0.5的圆柱形混凝土试件，混凝土试件的直径为10cm、高度为5cm，在养护箱(湿度98±2％，温度20±1℃)中养护28d。将养护后的混凝土试件侧面用环氧树脂密封，采用本发明装置进行水压力下混凝土淡水溶蚀和海水溶蚀与侵蚀试验。溶蚀介质分别为自来水(模拟淡水)和质量分数3.5％的氯化钠溶液(模拟海水)，试加的压强分别为0和1.0MPa，侵蚀时间分别设置为28、56、97、140d，在每个侵蚀时间取出混凝土试件分层取粉测试粉末中的钙离子含量和氯离子含量。140d后淡水和海水环境中混凝土的钙离子溶出速率和氯离子侵蚀速率分别如表4所示，结果表明海水中混凝土钙离子溶出速率大于淡水，并且压强能够增大钙离子溶出速率与氯离子侵蚀速率。Prepare multiple cylindrical concrete specimens with a water-cement ratio of 0.5. The diameter of the concrete specimens is 10cm and the height is 5cm. They are cured in a curing box (humidity 98±2%, temperature 20±1°C) for 28 days. The sides of the cured concrete specimens are sealed with epoxy resin, and the device of the invention is used to conduct concrete freshwater dissolution and seawater dissolution and erosion tests under water pressure. The corrosion media were tap water (simulated fresh water) and 3.5% sodium chloride solution (simulated seawater). The trial pressures were 0 and 1.0MPa respectively. The erosion times were set to 28, 56, 97, and 140 days respectively. Take out the concrete specimen after each erosion time and take powder in layers to test the calcium ion content and chloride ion content in the powder. The calcium ion dissolution rate and chloride ion erosion rate of concrete in fresh water and seawater environments after 140 days are shown in Table 4 respectively. The results show that the calcium ion dissolution rate of concrete in seawater is greater than that in fresh water, and pressure can increase the calcium ion dissolution rate and chloride ion erosion. rate.
表4淡水环境和海水环境下混凝土钙离子溶出速率和氯离子侵蚀速率
Table 4 Calcium ion dissolution rate and chloride ion erosion rate of concrete in freshwater environment and seawater environment
本发明通过对溶液增压以模拟水下区水泥基材料所面临的水头荷载作用，实现水头压力与钙离子溶蚀、氯离子侵蚀的协同作用，能够更准确反映水头压力作用下水下区水泥基材料钙离子溶出速率和氯离子侵蚀速率，从而能够更准确评价水头压力作用下水泥基材料的抗溶蚀与抗侵蚀性能。 The present invention simulates the head load faced by the cement-based materials in the underwater area by pressurizing the solution to achieve the synergistic effect of the water head pressure, calcium ion dissolution and chloride ion erosion, and can more accurately reflect the cement-based materials in the underwater area under the action of water head pressure. Calcium ion dissolution rate and chloride ion erosion rate can more accurately evaluate the anti-dissolution and anti-erosion properties of cement-based materials under the action of water head pressure.

Claims (7)

  1. 一种用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：包括试验仓以及用于为试验仓提供压力的空气压缩机；所述试验仓包括耐压仓和溶液存储仓，空气压缩机与耐压仓的连接气管上设有增压泵和压力传感器；在耐压仓内装有传感器组件，传感器组件通过固定装置固定在耐压仓上；所述传感器组件包括钙离子传感器、氯离子传感器和参比电极；在耐压仓和溶液存储仓的连接管道上设有泄压阀。A device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas, characterized by: including a test chamber and an air compressor used to provide pressure for the test chamber; the test chamber includes a pressure-resistant chamber and a solution storage bin. A booster pump and a pressure sensor are provided on the connecting air pipe between the air compressor and the pressure-resistant bin; a sensor component is installed in the pressure-resistant bin, and the sensor component is fixed on the pressure-resistant bin through a fixing device; the sensor component It includes a calcium ion sensor, a chloride ion sensor and a reference electrode; a pressure relief valve is provided on the connecting pipe between the pressure chamber and the solution storage chamber.
  2. 根据权利要求1所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：还包括PLC控制箱，增压泵、压力传感器、钙离子传感器、氯离子传感器和泄压阀分别通过电缆与PLC控制箱连接，PLC控制箱通过通讯模块与带显示屏的控制终端进行信息交互。The device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas according to claim 1, characterized in that: it also includes a PLC control box, a booster pump, a pressure sensor, a calcium ion sensor, a chloride ion The sensor and pressure relief valve are connected to the PLC control box through cables, and the PLC control box interacts with the control terminal with a display screen through the communication module.
  3. 根据权利要求1所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：所述耐压仓内填充有侵蚀溶液，侵蚀溶液为氯化铵和/或氯化钠溶液，溶液中，铵根离子的浓度为0～6mol/L，氯离子浓度为0～9mol/L。The device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas according to claim 1, characterized in that: the pressure-resistant chamber is filled with an erosion solution, and the erosion solution is ammonium chloride and/or Or sodium chloride solution. In the solution, the concentration of ammonium ions is 0~6mol/L and the concentration of chloride ions is 0~9mol/L.
  4. 根据权利要求3所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：所述耐压仓为有机玻璃或不锈钢耐压仓；向耐压仓灌注侵蚀溶液前，先将水泥基材料试件稳定放置于耐压仓内，所放入试件总体积不超过耐压仓体积的50％。The device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas according to claim 3, characterized in that: the pressure-resistant chamber is a plexiglass or stainless steel pressure-resistant chamber; and the pressure-resistant chamber is filled with Before eroding the solution, the cement-based material specimen shall be placed stably in the pressure chamber, and the total volume of the specimen placed shall not exceed 50% of the volume of the pressure chamber.
  5. 根据权利要求4所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：所述耐压仓内放置有水泥基材料试件，所述试件取粉方式为由暴露面向内逐层取粉，每层取粉厚度0.5～2mm；对取得的粉磨细后，使用X射线荧光光谱仪测定粉末中钙离子含量，同时用固液萃取法结合化学滴定法测定粉末中氯离子含量。The device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas according to claim 4, characterized in that: cement-based material specimens are placed in the pressure-resistant chamber, and the specimens are taken from The powder method is to extract powder layer by layer from the exposed surface inward, with a thickness of 0.5 to 2 mm for each layer; after grinding the obtained powder, use an X-ray fluorescence spectrometer to measure the calcium ion content in the powder, and use solid-liquid extraction combined with chemical titration. Method to determine the chloride ion content in powder.
  6. 根据权利要求1所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：所述钙离子传感器、氯离子传感器和参比电极用法兰方式安装在耐压仓顶部盖板上；钙离子传感器对溶液中钙离子浓度的测量范围10-5-10-1mol/L；氯离子传感器对溶液中氯离子浓度的测量范围为5×10-5-10-1mol/L；参比电极为二氧化锰固体参比电极；通过钙离子传感器和氯离子传感器实时得到侵蚀溶液中钙离子浓度和氯离子浓度，当侵蚀溶液中钙离子浓度或氯离子浓度达到平衡时，则更新耐压仓中的侵蚀溶液。The device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas according to claim 1, characterized in that: the calcium ion sensor, chloride ion sensor and reference electrode are flange-mounted on a resistant surface. On the top cover of the pressure chamber; the calcium ion sensor measures the calcium ion concentration in the solution in a range of 10 -5 -10 -1 mol/L; the chloride ion sensor measures the chloride ion concentration in the solution in a range of 5×10 -5 -10 -1 mol/L; the reference electrode is manganese dioxide solid reference electrode; the calcium ion concentration and chloride ion concentration in the etching solution are obtained in real time through the calcium ion sensor and the chloride ion sensor. When the calcium ion concentration or chloride ion concentration in the etching solution is When equilibrium is reached, the erosion solution in the pressure chamber is updated.
  7. 根据权利要求1所述的用于模拟水下区水泥基材料钙离子溶出和氯离子扩散情况的装置，其特征在于：所述溶液存储仓为有机玻璃制备而成，连接管道和连接气管的管路材质均为不锈钢波纹防爆编织管。 The device for simulating calcium ion dissolution and chloride ion diffusion of cement-based materials in underwater areas according to claim 1, characterized in that: the solution storage bin is made of organic glass, and the connecting pipe and the pipe connecting the trachea are The road materials are all stainless steel corrugated explosion-proof braided pipes.
PCT/CN2023/106510 2022-07-13 2023-07-10 Device for simulating calcium ion dissolution and chloride ion diffusion conditions of cement-based material in underwater area WO2024012393A1 (en)

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