CN112782211A - Water phase change detection method - Google Patents
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Abstract
The invention relates to a water phase change detection method, which comprises the steps of constructing an in-situ high-pressure detection device by utilizing a diamond anvil cell press, detecting the change of resistivity near a water phase interface under static pressure, recording the phenomenon of resistivity mutation caused by water phase change, determining melting curves of ice VI and ice VII and phase change curves of the ice VI and the ice VII, and judging the existence state, phase change and distribution of water according to water resistivity data; the conductivity of solid ice in the earth can be accurately detected by utilizing the metal electrode, the interference of a space charge layer effect on conductivity data is avoided, the phenomenon of resistivity mutation caused by water phase change is recorded, the measurement sensitivity is high, the precision is high, and the interference is not easy to occur.
Description
Technical Field
The invention relates to the field of high-pressure physical technology and material structures, in particular to a detection method for water phase change.
Background
Water is one of the most abundant and important substances in the nature and plays an important role in the process of global evolution. Water attacks the rock soil on earth, widely existing in silicate mantle in the form of hydroxyl groups, and shows many unique and even abnormal properties. The water in the deep part of the earth can influence the geophysical and geochemical processes such as the change of the physical and chemical properties of mineral rocks, the movement of plates, the convection of a mantle, the distribution of chemical elements of the earth and the origin of the earth, so that the understanding of the existence state, the phase change and the distribution of the water in the deep part of the earth has important significance for the understanding of the internal dynamic process and the geochemical evolution process of the earth.
The earth's interior is a complex high-temperature and high-pressure system, and since water is widely distributed in various forms in the earth's interior, it is important to study the electrical properties and phase diagram of water at high pressure and high temperature to further understand the properties of the materials in the earth's interior. In recent years, with the continuous perfection of high-temperature and high-pressure experimental equipment, the exploration of physical and chemical properties of substances at different temperatures and pressures is realized, the understanding of people on the boundary layer structures, compositions, dynamic processes and the like of the crust, the mantle and the nuclear mantle is promoted, and the cognition of people on the earth deep water circulation on the time and space scales is enriched.
At present, the ultra-high pressure experimental technology is divided into two major types: dynamic ultrahigh pressure experiment technology and static ultrahigh pressure experiment technology. The dynamic ultrahigh pressure experiment technology utilizes various detonation devices to generate impact pressure and simultaneously generates high temperature instantaneously, and is generally suitable for electrical characteristic research of molten state substances. Inside the earth, materials are generally in a state of static high pressure. Multiple high pressure experiments found that at room temperature, ice VI phase changed to ice VII at 2.1GPa in water.
Under the static high-pressure experimental condition, the phase change curves of ice obtained by different detection means are greatly different, and the experimental means can be divided into the following types:
(1) bridgman measured the change in volume of ice VI and ice VII with a piston-cylinder apparatus and determined the melting curve of ice below 3.9 GPa.
(2) An optical detection system is used for detecting the melting curve of ice by absorbing the obvious difference of the intensity of terahertz wave signals in two states of ice and water.
(3) The melting curve of ice VII in the range of 20-38GPa was determined using the appearance and disappearance of the X-ray diffraction peak (110) of ice VII.
(4) By means of Raman spectroscopy through OH-Stretching vibration frequency and H2O displacement, and detecting the melting curve of ice VII below 22 GPa.
(5) The melting curve of ice VII was determined using the change in strain sensitive resistance placed within the sample.
The dynamic high-voltage experiment is only used for transient research of liquid water electrical characteristics under the conditions of extremely high temperature and pressure; the melting curves obtained by different experimental criteria under static high pressure are different, and in the aspect of measuring the water electrical properties, the resistivity of water is indirectly measured by means of the strain sensitive material, so that the measurement sensitivity is weak, the precision is low, and the interference is easy to occur.
Disclosure of Invention
The invention provides a method for detecting water phase change under static high pressure through a conductivity change rule aiming at the problems in the prior art, which detects the resistivity change near a water phase interface under the static pressure, records the resistivity mutation phenomenon caused by the water phase change, determines the melting curves of ice VI and ice VII and the phase change curves of the ice VI and the ice VII, and judges the existence state, the phase change and the distribution of water according to the water resistivity data.
The technical scheme for realizing the invention is as follows: a water phase change detection method by using a diamond anvil cell press is characterized by comprising the following steps:
(1) starting a diamond anvil cell, enabling the upper diamond anvil cell to generate an indentation on the sealing gasket, arranging a through hole in the center of the indentation on the sealing gasket, and taking the through hole on the sealing gasket as a pressing cavity;
(2) chemically cleaning the diamond anvil by using sulfuric acid and nitric acid according to the volume ratio of 4:1 to remove grease and dust on the surface of the diamond anvil;
(3) depositing a 0.3 micron metal molybdenum film as a conductive layer on the anvil surface of the upper diamond anvil cell in a radio frequency sputtering mode for 4 minutes;
(4) processing the molybdenum film on the anvil surface of the upper diamond anvil cell into a van der Waals electrode pattern by using photoetching and chemical corrosion methods, wherein the arrangement position of the electrodes is completely determined by a precise photoetching machine console;
(5) depositing an aluminum oxide film of 1.5-2.5 microns on a molybdenum electrode on the anvil surface of the diamond anvil cell by using a radio frequency sputtering method to serve as an insulating layer;
(6) exposing an electrode detection window on the insulating layer by using a photoetching and chemical corrosion method, and respectively connecting four leads with a direct-current power supply and a voltmeter during detection;
(7) assembling a diamond anvil cell, arranging a sealing pad with a through hole on the anvil surface of a lower diamond anvil cell, firstly pressing a mica sheet with the thickness of 8 microns into a notch of a gasket, then placing ruby at the bottom of a pressing cavity, finally filling the pressing cavity with a deionized water dropping sample, and assembling an upper diamond anvil cell integrated with a microelectrode on a press to form an in-situ high-pressure detection device;
(8) at room temperature, a spanner is used for uniformly and slowly rotating a pressurizing screw to apply pressure to the sample, and the pressure is measured according to the fluorescence peak R of the ruby1Calibrating the pressure according to the frequency shift characteristic curve of the line along with the pressure;
(9) placing the in-situ high-pressure detection device into a convection furnace, calibrating the temperature by using two pairs of nickel-chromium thermocouples, placing a thermocouple 1 into the furnace to realize temperature measurement in the furnace, connecting a thermocouple 2 with a diamond anvil cell, measuring the temperature by using two thermocouples in a balanced manner to realize temperature regulation, and heating a deionized water drop sample to T by using the convection furnace1And keeping the temperature for 20 minutes;
(10) control T1Applying different pressures to the deionized water drop sample without changing, measuring the resistivity change curve of the deionized water drop sample under different pressures by adopting a Van der Pager method, and firstly, supplying an excitation current I to the two ends 1 and 2 of the upper diamond anvil cell integrated with the microelectrode12Measuring the voltage U across the terminals 3, 434To obtain a resistance R1＝U34/I12(ii) a Then the excitation current I is supplied at both ends 2 and 323Measuring the voltage U across the terminals 4, 141To obtain a resistance R2＝U41/I23R is to be1And R2The resistivity value ρ of the sample is calculated by substituting van der pol equation:
wherein d is the thickness of the deionized water drop sample measured by a micrometer; fitting out the curve T according to the abrupt change range of the curve of the resistivity along with the change of the pressure1First derivative of resistivity with pressure change under conditions, derivative curve peak pressure P1I.e. at T1Phase change pressure of the deionized water drop sample at temperature;
(11) raising to different temperatures T using convection ovensnDetermining T by the method in step (10)nPhase transition pressure P of deionized water drop samplenObtaining a plurality of pairs of phase change data points (T)n,Pn)；
(12) At room temperature, a spanner is used for uniformly and slowly rotating a pressurizing screw to apply pressure to the deionized water drop sample, and according to the ruby fluorescence peak R1Calibrating the pressure according to the frequency shift characteristic curve of the line along with the pressure, and applying a certain pressure P to the deionized water drop sample1' pressurizing and solidifying the liquid sample, and keeping the pressure P1Putting the diamond anvil cell press into a convection furnace, heating the solidified sample, measuring the resistivity of the sample in deionized water at different temperatures by adopting a Van der Pauw method, and fitting the resistivity in P according to the mutation range of a curve of the resistivity along with the temperature change1First derivative of resistivity with temperature at condition, derivative curve peak temperature T1That is to say in P1The melting temperature of the sample of deionized water drops under pressure;
(13) applying different pressures P to a sample of deionized water dropletsn' measuring PnPhase transition temperature T of deionized water droplet samplenObtaining pairs of melting data points (T)n＇,PnMin.), according to the measured phase variable data points (T) of the deionized water droplet samplesn,Pn) And melting data point (T)n＇,Pn' to get a sample of deionized water droplets.
In the step (1), the diamond anvil press presses a T-301 steel sheet with the thickness of 250 microns into a 100-micron indentation, and a hole with the diameter of 400 microns is burned at the center of the indentation by laser to serve as a pressing cavity.
The water phase change detection method has the beneficial effects that:
1. a detection method of water phase change can accurately detect the conductivity of solid ice in the earth by utilizing a metal electrode, avoid the interference of a space charge layer effect on conductivity data, record the phenomenon of resistivity mutation caused by water phase change, and determine melting curves of ice VI and ice VII and phase change curves of the ice VI and the ice VII;
2. a detection method for water phase change judges the existence state, phase change and distribution of water according to water resistivity data, and has the advantages of strong measurement sensitivity, high precision and difficult interference.
Drawings
FIG. 1 is a schematic diagram of an in-situ high pressure detection device employed in a method of detecting a water phase change;
FIG. 2 is a view of the diamond anvil A on the piece 6 of the in-situ high pressure test apparatus of FIG. 1;
FIG. 3 is a schematic diagram of the integrated microcircuits on the anvil surface of the diamond anvil cell 6 of the in-situ high voltage testing apparatus of FIG. 1;
FIG. 4 is a diagram of an in-situ high pressure detection device disposed within a convection oven during heating;
FIG. 5 is a schematic diagram showing the change law of the resistivity of a water sample under the action of certain temperature and different pressure;
FIG. 6 is a schematic diagram showing the change law of the resistivity of a water sample under the action of certain pressure and different temperatures;
FIG. 7 is a three-phase diagram of water;
in the figure: 1. the micro-electrode comprises a micro-electrode first end, 2 micro-electrode second end, 3 micro-electrode third end, 4 micro-electrode fourth end, 5 sample, 6 upper diamond anvil, 7 lower diamond anvil, 8 ruby, 9 sealing pad, 10 copper wire, 11 aluminum oxide, 12 molybdenum.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific embodiments, which are described herein for illustrative purposes only and are not intended to limit the present invention.
With reference to the accompanying drawings 1-3, the in-situ high-pressure detection device is constructed and constructed as follows:
(1) pre-pressing a T-301 steel sheet with the thickness of 250 microns into a 100-micron indentation by using a diamond anvil cell pressing machine, and burning a hole with the diameter of 400 microns at the center of the indentation by using laser to serve as a pressing cavity;
(2) chemically cleaning the diamond anvil by using sulfuric acid and nitric acid according to the volume ratio of 4:1, and removing grease and dust on the surface to improve the adhesive force of the metal conductive film on the diamond anvil;
(3) depositing a metal molybdenum film as a conductive layer on the anvil surface of the upper diamond anvil cell in a radio frequency sputtering mode, wherein the deposition time is 4 minutes, and the thickness of the molybdenum film is 0.3 micron;
(4) processing the metal molybdenum film into a pattern of a van der Waals electrode by utilizing a photoetching and chemical corrosion method;
(5) depositing an alumina film of 2 microns on the molybdenum electrode by using a radio frequency sputtering method to serve as an insulating layer;
(6) then exposing the electrode detection window by using a photoetching and chemical corrosion method, and leading out a copper wire;
(7) pressing 8 micron thick mica sheets into the dents;
(8) assembling the upper diamond anvil integrated with the microelectrode on a press;
(9) placing ruby at the bottom of the pressure cavity, and dripping deionized water into the pressure cavity;
with reference to figure 4 of the drawings,
(10) placing the in-situ high-pressure detection device into a convection furnace, calibrating the temperature by using two pairs of nickel-chromium thermocouples, placing a thermocouple 1 into the furnace to realize temperature measurement in the furnace, connecting a thermocouple 2 with a diamond anvil cell, measuring the temperature by using two thermocouples in a balanced manner to realize temperature regulation, and heating a deionized water drop sample to T by using the convection furnace1And keeping the temperature for 20 minutes;
(11) at room temperature, a spanner is used for uniformly and slowly rotating a pressurizing screw to apply pressure to the sample, and the pressure is measured according to the fluorescence peak R of the ruby1Calibrating the pressure according to the frequency shift characteristic curve of the line along with the pressure;
(12) use ofHeating deionized water to T by convection furnace1And keeping the temperature for 20 minutes;
(13) control T1And (4) applying different pressures to the water without changing, and measuring the resistivity change curve of the deionized water under different pressures by adopting a Van der Pauw method. Firstly, excitation current I is supplied to two ends of a first end 1 and a second end 2 of an upper diamond anvil integrated microelectrode12Measuring voltage U at the third end 3 and the fourth end 434To obtain a resistance R1＝U34/I12(ii) a Then the excitation current I is supplied to the second end 2 and the third end 323Measuring the voltage U at the fourth end 4 and the first end 141To obtain a resistance R2＝U41/I23R is to be1And R2The electric lease value ρ of the sample is calculated by substituting van der pol equation:
wherein d is the thickness of the sample, and the thickness is measured by a micrometer in the experiment to realize in-situ measurement of the water resistivity;
(14) fitting out the curve T according to the abrupt change range of the curve of the resistivity along with the change of the pressure1First derivative of resistivity with pressure change under conditions, derivative curve peak pressure P1I.e. at T1Phase transition pressure of deionized water at temperature;
(15) raising to different temperatures T using convection ovensnMeasuring TnPhase transition pressure P of the sewagenObtaining a plurality of pairs of phase change data points (T)n,Pn)；
(16) Applying a certain pressure P to the deionized water1' freezing water to ice;
(17) maintaining the pressure P1Putting the in-situ high-voltage detection device into a convection furnace, heating ice, and measuring the water resistivity at different temperatures by adopting a van der Waals method;
(18) fitting out the curve P according to the abrupt change range of the change curve of the resistivity along with the temperature1First derivative of resistivity with temperature at condition, peak of derivative curveValue temperature T1That is to say in P1"melting temperature of ice under pressure;
(19) applying different pressures P to ice using high pressure meansn' measuring PnPhase transition temperature T of bottom samplen' obtaining several pairs of ice melting data points (T)n＇,Pn＇)；
(20) Based on the measured water phase variable data points (T)n,Pn) And melting data point (T) of icen＇,Pn' to make water, drawing a three-phase diagram of water, and determining the three-phase points of water.
Referring to fig. 5, it can be seen from the relationship between the resistivity of a water sample and the pressure change at a certain temperature that, under the condition of 340K, when the pressure is 2.09GPa, the resistivity of water changes abruptly, the resistivity derivative curve shows a single peak, and the ice VI changes into the ice VII. 2.09GPa is the phase transition pressure of the ice at 340K, and the phase transition data point is marked as (340, 2.09).
Referring to the attached figure 6, it can be known from the relationship of the resistivity of the ice sample with the temperature change under a certain pressure that under the conditions of 1.2GPa, 2.2GPa and 2.9GPa, the temperature rises to a narrow range, the conductivity of the ice rises sharply by 1-2 orders of magnitude, a derivative fitting curve of the resistivity appears a single peak, and the ice melts into water. The temperature at which a single peak occurs is the melting temperature of ice at the corresponding pressure, and the melting data points are (310, 1.2), (360, 2.2), (410, 2.9), respectively.
Referring to fig. 7, under different temperature and pressure conditions, several pairs of phase change data points and melting data points of water are measured, and finally a three-phase diagram of the water is fitted as shown in the figure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (2)
1. A water phase change detection method by using a diamond anvil cell press is characterized by comprising the following steps:
(1) starting a diamond anvil cell, enabling the upper diamond anvil cell to generate an indentation on the sealing gasket, arranging a through hole in the center of the indentation on the sealing gasket, and taking the through hole on the sealing gasket as a pressing cavity;
(2) chemically cleaning the diamond anvil by using sulfuric acid and nitric acid according to the volume ratio of 4:1 to remove grease and dust on the surface of the diamond anvil;
(3) depositing a 0.3 micron metal molybdenum film as a conductive layer on the anvil surface of the upper diamond anvil cell in a radio frequency sputtering mode for 4 minutes;
(4) processing the molybdenum film on the anvil surface of the upper diamond anvil cell into a van der Waals electrode pattern by using photoetching and chemical corrosion methods, wherein the arrangement position of the electrodes is completely determined by a precise photoetching machine console;
(5) depositing an aluminum oxide film of 1.5-2.5 microns on a molybdenum electrode on the anvil surface of the diamond anvil cell by using a radio frequency sputtering method to serve as an insulating layer;
(6) exposing an electrode detection window on the insulating layer by using a photoetching and chemical corrosion method, and respectively connecting four leads with a direct-current power supply and a voltmeter during detection;
(7) assembling a diamond anvil cell, arranging a sealing pad with a through hole on the anvil surface of a lower diamond anvil cell, firstly pressing a mica sheet with the thickness of 8 microns into a notch of a gasket, then placing ruby at the bottom of a pressing cavity, finally filling the pressing cavity with a deionized water dropping sample, and assembling an upper diamond anvil cell integrated with a microelectrode on a press to form an in-situ high-pressure detection device;
(8) at room temperature, a spanner is used for uniformly and slowly rotating a pressurizing screw to apply pressure to the sample, and the pressure is measured according to the fluorescence peak R of the ruby1Calibrating the pressure according to the frequency shift characteristic curve of the line along with the pressure;
(9) placing the in-situ high-pressure detection device into a convection furnace, calibrating the temperature by using two pairs of nickel-chromium thermocouples, placing a thermocouple 1 into the furnace to realize temperature measurement in the furnace, connecting a thermocouple 2 with a diamond anvil cell, measuring the temperature by using two thermocouples in a balanced manner to realize temperature regulation, and heating a deionized water drop sample to T by using the convection furnace1And keeping the temperature for 20 minutes;
(10) controlSystem of T1Applying different pressures to the deionized water drop sample without changing, measuring the resistivity change curve of the deionized water drop sample under different pressures by adopting a Van der Pager method, and firstly, supplying an excitation current I to the two ends 1 and 2 of the upper diamond anvil cell integrated with the microelectrode12Measuring the voltage U across the terminals 3, 434To obtain a resistance R1＝U34/I12(ii) a Then the excitation current I is supplied at both ends 2 and 323Measuring the voltage U across the terminals 4, 141To obtain a resistance R2＝U41/I23R is to be1And R2The resistivity value ρ of the sample is calculated by substituting van der pol equation:
wherein d is the thickness of the deionized water drop sample measured by a micrometer; fitting out the curve T according to the abrupt change range of the curve of the resistivity along with the change of the pressure1First derivative of resistivity with pressure change under conditions, derivative curve peak pressure P1I.e. at T1Phase change pressure of the deionized water drop sample at temperature;
(11) raising to different temperatures T using convection ovensnDetermining T by the method in step (10)nPhase transition pressure P of deionized water drop samplenObtaining a plurality of pairs of phase change data points (T)n,Pn)；
(12) At room temperature, a spanner is used for uniformly and slowly rotating a pressurizing screw to apply pressure to the deionized water drop sample, and according to the ruby fluorescence peak R1Calibrating the pressure according to the frequency shift characteristic curve of the line along with the pressure, and applying a certain pressure P to the deionized water drop sample1' pressurizing and solidifying the liquid sample, and keeping the pressure P1Putting the diamond anvil cell press into a convection furnace, heating the solidified sample, measuring the resistivity of the sample in deionized water at different temperatures by adopting a Van der Pauw method, and fitting the resistivity in P according to the mutation range of a curve of the resistivity along with the temperature change1First derivative of resistivity with temperature at condition, peak of derivative curveValue temperature T1That is to say in P1The melting temperature of the sample of deionized water drops under pressure;
(13) applying different pressures P to a sample of deionized water dropletsn' measuring PnPhase transition temperature T of deionized water droplet samplenObtaining pairs of melting data points (T)n＇,PnMin.), according to the measured phase variable data points (T) of the deionized water droplet samplesn,Pn) And melting data point (T)n＇,Pn' to get a sample of deionized water droplets.
2. The method according to claim 1, wherein in the step (1), the diamond anvil press pre-presses a T-301 steel sheet with a thickness of 250 microns into a 100 micron indentation, and a laser is used to burn a hole with a diameter of 400 microns at the center of the indentation as a pressing cavity.
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