CN113655047B - Method for determining alpha-beta phase transition P-T relation of quartz - Google Patents

Method for determining alpha-beta phase transition P-T relation of quartz Download PDF

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CN113655047B
CN113655047B CN202110831716.6A CN202110831716A CN113655047B CN 113655047 B CN113655047 B CN 113655047B CN 202110831716 A CN202110831716 A CN 202110831716A CN 113655047 B CN113655047 B CN 113655047B
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李建康
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Institute of Mineral Resources of Chinese Academy of Geological Sciences
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Abstract

The invention discloses a method for determining a P-T relation of alpha-beta phase transformation of quartz, which comprises the following steps: obtaining the phase transition temperature Ttr of the quartz beta 0-beta 1 and the corresponding phase transition pressure Ptr of the quartz alpha-beta; determining the quartz alpha-beta phase transition P-T relation according to the quartz alpha-beta phase transition temperature Ttr and the corresponding quartz alpha-beta phase transition pressure Ptr, and expressing as follows: ptr (. + -. 5.6MPa) ═ 0.0008. Ttr2+2.8056 · Ttr-1877.5; wherein the alpha-beta phase transition temperature Ttr of the quartz is that the quartz is 128cm‑1The characteristic peak of the Raman peak reaches the temperature when the Raman peak reaches the stable temperature, and Ttr is more than or equal to 574 ℃ and less than or equal to 889 ℃. The determination method is simple and easy to implement, the accuracy of pressure calibration can be obviously improved, and the obtained quartz alpha-beta phase transition P-T relation can be applied to H2The O system is used in the experimental determination of PVT parameters under high temperature and high pressure, and can be further popularized to the determination of H-containing2PVT data of binary and multi-element system geological fluid of O under high temperature and high pressure for establishing geological fluid containing H2And the equation of state of the O binary and multi-element system geological fluid lays a foundation.

Description

Method for determining alpha-beta phase transition P-T relation of quartz
Technical Field
The invention relates to the field of high-temperature and high-pressure experiments, in particular to a method for determining a P-T relation of alpha-beta phase transition of quartz.
Background
The alpha-beta phase transformation phenomenon of quartz was first observed by Le Chatelier in 80 s of 19 th century, and scientists have conducted a great deal of research on the alpha-beta phase transformation phenomenon because the alpha-beta phase transformation phenomenon has important tracing and indicating significance in relevant research. Initial research efforts focused primarily on the observation and measurement of changes in optical properties that occur when quartz undergoes an alpha-beta transformation at a pressure of 0.1 MPa. Later, with the advent of high temperature and high pressure equipment (e.g., Piston Cylinder Piston-Cylinder Apparatus, Anvil-opposing Device, Diamond-pressed and inverted-shaped Cell, etc.), the focus of the research has shifted to experimental determination of the P-T relationship for the alpha-beta phase transition of quartz. At present, the experimental methods used for measuring the alpha-beta phase transition boundary line of quartz under the condition that the pressure is more than or equal to 0.1MPa mainly comprise a thermal difference analysis method, a pressure difference analysis method, an interference color analysis method and a laser Raman spectrum analysis method. The thermal difference analysis method and the differential pressure analysis method have the advantages that the temperature and the pressure during the alpha-beta phase transition of the quartz can be directly measured, and the defect is that the error of test data is large; the interference color analysis method has the advantages of simplicity, convenience and feasibility, and can be used for analyzing the change of the interference color on the surface of the quartz by only observing the change of the interference color on the surface of the quartz under a microscope by naked eyes without other spectral analysis equipment, but the method has higher requirements on the thickness of an analysis sample and the direction of incident light, so the measurement precision is not high; the laser Raman spectroscopy analysis method is an analysis method combining a diamond pressure chamber and a micro confocal Raman spectrometer, and has the advantages of high test precision and simple sample preparation, so the method is very suitable for in-situ determination of quartz alpha-beta phase change P-T parameters.
The results of the parameters of the quartz alpha-beta phase transition P-T obtained by different researchers by using different, even the same experimental test methods are all greatly different, and the reason is mainly caused by the low measurement precision of the equipment, for example, the temperature measurement error of the quartz alpha-beta phase transition temperature obtained by the thermal difference method and the pressure difference method of Mirwald and Massonne (1980) is +/-3 ℃. In addition, there are errors caused by objective artifacts in the process of processing experimental data. Therefore, the hydrothermal diamond pressure cavity is combined with the confocal microscopy Raman spectrometer to carry out systematic experimental study on the temperature of alpha-beta phase change of quartz under different pressure conditions, and a new method for determining the P-T relation of the alpha-beta phase change of quartz is provided, so as to lay a foundation for more accurately defining the P-T parameter of the alpha-beta phase change of quartz.
Disclosure of Invention
The invention aims to provide a method for determining the P-T relation of the alpha-beta phase transition of quartz.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for determining the P-T relation of quartz alpha-beta phase transformation, which is characterized by comprising the following steps:
obtaining the quartz alpha-beta phase transition temperature Ttr and the corresponding quartz alpha-beta phase transition pressure Ptr;
determining the quartz alpha-beta phase transition P-T relation according to the quartz alpha-beta phase transition temperature Ttr and the corresponding quartz alpha-beta phase transition pressure Ptr, and expressing as follows:
Ptr(±5.6MPa)＝0.0008·Ttr2+2.8056·Ttr-1877.5；
wherein the alpha-beta phase transition temperature Ttr of the quartz is that the quartz is 128cm-1The characteristic peak of the Raman peak reaches the temperature when the Raman peak reaches the stable temperature, and Ttr is more than or equal to 574 ℃ and less than or equal to 889 ℃.
The alpha-beta phase transition temperature Ttr of the quartz is that the quartz is 128cm-1The temperature at which the characteristic peak of the Raman peak position is stabilized means that the quartz is at 128cm-1Temperature at which the raman peak position no longer shifts continuously with increasing temperature and pressure.
The prior art discloses quantitative research quartz 464cm by combining a diamond pressure cavity and a micro-confocal Raman spectrometer-1The relationship between the Raman peak frequency shift and the alpha-beta quartz phase transition temperature pressure can improve the accuracy of determining the alpha-beta phase transition boundary of quartz to a certain extent, but the invention discovers that when the variation of the external pressure and the external temperature are the same, the quartz is 128cm-1The frequency variation of the Raman peak is about 464cm-1The change of Raman peak frequency is more than 5 times, so that the quartz is used at 128cm-1The variation relation of the Raman peak frequency shift with the temperature obtains the quartz alpha-beta phase transition temperature Ttr, and the precision of determining the alpha-beta phase transition boundary of the quartz can be further improved.
Further, the quartz alpha-beta phase transition temperature Ttr is measured by combining a hydrothermal diamond pressure cavity with a laser Raman spectrometer.
Further, the hydrothermal diamond pressure cavity is a Bassett type hydrothermal diamond pressure cavity; the laser Raman spectrometer is a micro confocal Raman spectrometer.
Further, the method for obtaining the quartz α - β transformation temperature Ttr and the corresponding quartz α - β transformation pressure Ptr comprises the following steps (1) or (2):
step (1), when the phase transition pressure Ptr of quartz alpha-beta is 0.1MPa,
putting a quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, wherein the sample cavity is not required to be sealed, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, starting heating, and observing that the quartz sample is 128cm in the heating process-1Continuously shifting the characteristic peak of the Raman peak position to the direction with small wave number, and recording the temperature when the characteristic peak is not continuously shifted to the direction with small wave number as the quartz alpha-beta phase transition temperature Ttr;
step (2), when the phase transition pressure Ptr of the quartz alpha-beta is more than 0.1MPa,
s1, putting the deionized water and the quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
s2, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer; heating, and recording the disappearance temperature Th of bubbles in the sample cavity1Meanwhile, the quartz sample is observed to be 128cm in the temperature rising process-1The characteristic peak of the Raman peak position is shifted continuously in the direction of small wave number, and the temperature Ttr at which the characteristic peak is not shifted continuously in the direction of small wave number is recorded1；
S3, pausing the temperature rise and slowly reducing the temperature, when bubbles in the sample cavity are observed to reappear, slowly raising the temperature again and recording the disappearance temperature Th of the reappeared bubbles2Meanwhile, the quartz sample is observed to be 128cm in the temperature rising process-1The characteristic peak of the Raman peak position is shifted continuously in the direction of small wave number, and the temperature Ttr at which the characteristic peak is not shifted continuously in the direction of small wave number is recorded2；
S4, comparing the bubble disappearance temperature Th1And bubble disappearance temperature Th2And carrying out the following steps a and b;
a. when bubble disappearance temperature Th1And bubble disappearance temperature Th2The same or different by less than or equal to 2 ℃, the temperature Ttr2Namely the quartz alpha-beta phase transition temperature Ttr; then obtaining corresponding quartz alpha-beta phase transition pressure Ptr according to an IAPWS-95 pure water multi-parameter state equation;
b. when bubble disappearance temperature Th1And bubble disappearance temperature Th2The difference is greater than 2 deg.C, steps S1-S4 are repeated.
According to the specific embodiment of the invention, the step (1) further comprises a training operation of the metal gasket, wherein the training operation can be performed before the hydrothermal diamond pressure chamber is connected with the laser raman spectrometer, or after the hydrothermal diamond pressure chamber is connected with the laser raman spectrometer, or can be performed independently, or can be performed simultaneously with the determination of the quartz alpha-beta phase transition temperature Ttr; the method specifically comprises the following steps:
heating, and recording the disappearance temperature Th of bubbles in the sample cavity1Then, the temperature is reduced after the temperature rise is suspended, when the bubbles in the sample cavity are observed to reappear, the temperature rise is slowly carried out again, and the reappeared bubble disappearance temperature Th is recorded2(ii) a Circulating the steps until adjacent bubble disappearance temperatures Th are continuously carried out twicenAnd Thn+1And the same or the difference is less than 2 ℃, the training of the rhenium sheet is finished. Wherein, training metal gasket can make metal gasket reach steady state to guarantee the isochoricity in sample chamber, and the metal gasket that does not pass through the high temperature training can take place to warp at the experimentation.
Further, the temperature increasing process of step (1) or S2 of step (2) or S3 of step (2) specifically includes the following steps:
in the temperature range from room temperature to 300 ℃, the heating rate of 20-30 ℃/min is adopted; the temperature range of 300-500 ℃ adopts the temperature rise rate of 10-15 ℃/min; the temperature rise rate of 5-8 ℃/min is adopted above 500 ℃, and the temperature rise rate is 1-4 ℃/min when the temperature rises to the alpha-beta transformation point of quartz.
Further, before the hydrothermal diamond pressure chamber in the step (1) or the step (2) is connected with the laser raman spectrometer, the linear calibration of the laser raman spectrometer is further included.
The invention has the following beneficial effects:
the invention utilizes hydrothermal diamond pressure chamber (HDAC) combined with laser Raman to quantitatively research 128cm quartz-1The relationship between the Raman peak frequency shift and the alpha-beta quartz phase transition temperature and pressure provides a novel method for determining the alpha-beta quartz phase transition P-T relationship, and the method can obviously improve the accuracy of pressure calibration.
In the quartz alpha-beta phase transition P-T relation provided by the invention, R20.9998. The relationshipThe range of the formula applicable to temperature and pressure conditions is expanded to T<900℃，P<1.2Gpa。
The method for determining the quartz alpha-beta phase transition P-T relation is simple and easy to implement and high in precision, and the quartz alpha-beta phase transition P-T relation obtained by the method can be applied to H2The O system is used in the experimental determination of PVT parameters under high temperature and high pressure, and can be further popularized to the determination of H-containing2PVT data of binary and multi-element system geological fluid of O under high temperature and high pressure for establishing geological fluid containing H2The equation of state of the binary and multi-element system geological fluid of O lays a foundation.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows the Raman spectra taken at different temperatures during the temperature increase of example 1.
FIG. 2 shows the transformation of the quartz of example 1 from the alpha phase to the beta phase at 128cm-1And 465cm-1A characteristic peak of the Raman peak position is in a change relation graph with temperature; wherein A shows the transition of quartz from alpha phase to beta phase at 128cm at a temperature below 600 deg.C-1And 465cm-1A characteristic peak of the Raman peak position is in a graph with the change of temperature; b shows that the temperature is in the range of 540-600 ℃, and the quartz is converted from alpha phase to beta phase at 128cm-1And 465cm-1And (3) a characteristic peak of the Raman peak position is in a graph with the change of temperature.
FIG. 3 shows the Raman spectra of example 2 at different temperatures during the temperature increase.
FIG. 4 shows the transformation of the quartz of example 2 from the alpha phase to the beta phase at 128cm-1And 465cm-1A characteristic peak of the Raman peak position is in a graph with the change of temperature; wherein A shows that at a temperature below 725 ℃, the quartz changes from the alpha phase to the beta phase at 128cm-1And 465cm-1A characteristic peak of the Raman peak position is in a graph with the change of temperature; b shows that the temperature is in the range of 695-DEG-725 ℃, and the quartz is converted into a beta-phase from an alpha phase at 128cm-1And 465cm-1And (3) a characteristic peak of the Raman peak position is in a graph with the change of temperature.
FIG. 5 is a schematic diagram showing the variation of the P-T trajectory in the cavity of the HDAC sample during temperature increase in example 2; wherein, panel A shows the state diagram of the HDAC-VT sample cavity at point 1; panel B shows a schematic of the state of the HDAC-VT sample chamber at point 2.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The hydrothermal diamond pressure chamber and Raman spectrometer used in the following examples are Bassett hydrothermal diamond pressure chamber (HDAC-VT) and HORIBA Jobin Yvon confocal LabRAM HR Evolution confocal Raman spectrometer with three guide columns, respectively.
The quartz samples used in the following examples were quartz crystal slices from pegmatite belts from astrakalite beryllite deposits, Xinjiang.
Example 1: determination of quartz alpha-beta phase transition temperature Ttr under 0.1MPa pressure
The experimental steps of the group of experiments are mainly divided into four main steps of preparation before sample loading, temperature rise, acquisition of Raman spectrum at constant temperature and the like.
Preparation work before sample loading: the method mainly comprises two aspects of quartz sample preparation and sample cavity preparation, wherein the quartz sample preparation process comprises the following steps: firstly, unloading a quartz crystal slice from a glass slide, wiping off residual organic glue on the contact surface of the quartz slice and the glass slide by using high-purity alcohol, then taking a small sample on the quartz slice, and cutting the sample into the size required by loading the sample into an HDAC-VT sample cavity, thus obtaining the quartz sample. The preparation of the sample cavity mainly comprises the steps of cleaning a metal rhenium pad, cleaning a diamond anvil surface, fixing the rhenium pad on the diamond anvil surface below the rhenium pad and the like;
loading of the sample: the process is relatively simple, only a quartz sample prepared in advance needs to be put into the HDAC-VT sample cavity, and water does not need to be added into the HDAC-VT sample cavity. In addition, the sample cavity is not sealed (namely the diamond anvil block on the sample cavity is not pressed with the rhenium metal gasket) so as to ensure that the pressure in the sample cavity can be kept about 0.1MPa all the time in the temperature rising process;
and (3) acquiring Raman spectra at a temperature rise and a constant temperature: after the sample is loaded, the sample can be moved to a laser micro-confocal Raman spectrometer to heat the sample, the temperature is kept constant for about 4 minutes after the temperature reaches the temperature value required by the experiment, and then the Raman spectrum at the temperature is acquired in situ. Collecting a Raman spectrum at intervals during the temperature rise (single window collection at 320 cm)-1Wavenumber centered, the resulting Raman spectrum ranged from about 77cm-1To 593cm-1) As shown in detail in figure 1. Wherein, in the temperature rise process, the temperature rise rate of 20 ℃/min is adopted in the temperature range from room temperature to 300 ℃; in the temperature range of 300 ℃ and 500 ℃, the heating rate of 10 ℃/min is adopted; the temperature rise rate of 5 ℃/min is adopted above 500 ℃, the temperature rise rate is reduced to 1 ℃/min when the temperature rises to the alpha-beta transformation point of the quartz, and the quartz is observed to be 128cm in the temperature rise process-1The characteristic peak of the Raman peak position continuously shifts to the direction of small wave number, and the temperature when the characteristic peak does not continuously shift to the direction of small wave number is recorded as the quartz alpha-beta phase transition temperature Ttr.
As can be seen from fig. 1: 1) after analyzing the quartz Raman spectrum under the conditions of 0.1MPa and 24.2 ℃, the quartz characteristic Raman peak (465 cm) collected in the experiment is found-1、206cm-1、128cm-1、355cm-1、264cm-1、403cm-1And 520cm-1) Only 128cm in-1And 465cm-1The two main Raman peaks have stronger peak heights, and the spectrum collection temperature always exists in the range of 24-600 ℃ and keeps the relatively stronger peak heights.
2) Starting from room temperature, with a gradual increase in temperature, 128cm of alpha-quartz-1The shift of the raman peak gradually shifts in the direction of small wave number. When the temperature is raised to the lowest temperature (573.8 + -0.2 deg.C) required for beta-phase quartz, the alpha-quartz is 128cm-1The shift of the Raman peak is shifted to 96.5. + -. 1.5cm-1Thereafter, the raman shift of the raman peak no longer shifts significantly with increasing temperature. Further, during the gradual temperature rise from room temperature, α -quartz 465cm-1The Raman peak shift is first gradually shifted toward smaller wavenumbers, and then reduced to 458cm-1The value is temporarily kept unchanged after left and right until 458cm is reached when the temperature is increased to be close to the alpha-beta phase transition temperature point of quartz-1The Raman shift of the Raman peak is rapidly increased to 459cm-1No significant change then occurs with increasing temperature.
As can be seen from FIG. 2, the quartz is at 128cm after the temperature is raised to the range of 550 ℃ and 580 DEG C-1The frequency variation of the Raman peak is much higher than that at 464cm-1The Raman peak frequency changes, so that the quartz is at 128cm-1The crystal alpha-beta phase transition temperature Ttr obtained by the relationship of the Raman peak frequency shift with the temperature change is more accurate.
Discussion: the influence of the thickness of the quartz sample or (and) the incident direction of the white light source and the like can cause that when the quartz is converted from the alpha phase to the beta phase in the temperature rising process, the phenomenon of sudden movement of the interference color on the surface of the quartz is not observed, so that the alpha-beta phase transition temperature of the quartz cannot be determined by using the interference color method. The determination of the quartz alpha-beta phase transition temperature Ttr in the experiment is based on the main Raman characteristic peak (128 cm) of the quartz-1) The temperature variation relationship is determined. When the quartz is converted from the alpha phase to the beta phase, the refractive index and the internal structure of the quartz sample are subjected to mutation, and the displacement of the Raman characteristic peak of the quartz is also subjected to corresponding change. As can be seen in FIG. 1, the quartz is 128cm-1And 465cm-1The shifts of the two raman peaks are mutated at 574 ℃ and 564 ℃ respectively and then the values are kept constant, so the quartz α - β phase transition temperature should be 574 ℃ or 564 ℃. The results of the previous studies show that the temperature of quartz alpha-beta transformation under 0.1MPa is mainly concentrated between 570.7 ℃ and 574.4 ℃, therefore, the experiment in this group should obtain the temperature of quartz alpha-beta transformation of 573.8 +/-0.2 ℃ under 0.1 MPa. This conclusion also confirms that the sample is 128c from quartzm-1The quartz alpha-beta phase transition temperature Ttr obtained by the Raman peak frequency shift along with the change of the temperature is more accurate.
Example 2: determination of quartz alpha-beta phase transition temperature Ttr under high pressure condition
The procedure for measuring the crystal α - β transformation temperature under high pressure is substantially the same as that for measuring the crystal α - β transformation temperature under 0.1MPa pressure, except that when the sample is loaded, the substance added to the HDAC-VT sample chamber contains deionized water in addition to the crystal sample, and the two substances are completely sealed in the HDAC-VT sample chamber (i.e., the upper and lower diamond press anvils are pressed against the rhenium metal pad), and at this time, a crystal wafer (denoted as Q), liquid water, and a bubble (denoted as v) are present in the HDAC-VT sample chamber (as shown in fig. 5, panel a). The volume of the bubble gradually decreases with a gradual increase in temperature, and the temperature Th at which the bubble disappears completely is recorded1I.e., the first uniform temperature (the state of the HDAC-VT sample chamber at which the bubbles completely disappeared is shown in panel B of fig. 5). With continued heating, the temperature and pressure of the homogeneous system in the sample chamber will theoretically follow the line Th in FIG. 51The corresponding isovolumetric line 1 moves, but since the new metal pad is not subjected to the pressure compression training, the volume of the sample chamber usually decreases by no more than 0.5% (occasionally, the volume of the sample chamber also increases), so that actually the homogeneous P-T trajectory in the HDAC-VT sample chamber (wherein the P-T trajectory in the HDAC-VT sample chamber is plotted according to the IAPWS-95 pure water multi-parameter equation of state) will gradually increase along the arrow direction from point 2 to point 3 in fig. 5 until the quartz undergoes the α - β phase transition (the determination method is the same as in embodiment 1), and the first α - β phase transition temperature Ttr is obtained at this time1(as shown by point 3 in fig. 5). Next, a slow cooling is performed, and when the temperature is slightly lower than the temperature corresponding to point 4 in fig. 1, a contracted bubble appears in the HDAC-VT sample chamber. Then, heating is performed again, and when the temperature rises to the temperature corresponding to point 4 in FIG. 5, the bubbles in the HDAC-VT sample chamber disappear again, and a second uniform temperature Th is obtained2. The temperature is continuously increased, the metal gasket is trained in the last temperature increasing and decreasing process,the volume change property of the sample chamber tends to be further stabilized, and the uniform system P-T track after being homogenized again moves to the position of point 5 in FIG. 5 along the arrow direction shown from point 4 to point 5 in FIG. 5, and the second quartz alpha-beta phase transition temperature Ttr is obtained2. The temperature of the system is then lowered to a point slightly below point 6 in figure 5, at which point bubbles again appear in the sample chamber. Immediately after the third round of temperature rise, the bubble in the sample chamber disappears when the temperature rises to the position of point 6 in fig. 5, and a third uniform temperature value Th is obtained3Continuously raising the temperature to obtain a third quartz alpha-beta phase transition temperature Ttr3. After the training of the two previous heating and cooling processes, the physical properties of the metal gasket are basically stable, so the Th2And Th3Equal or less than or equal to 2 ℃, and re-circulating if the disappearance temperature Th of the bubbles in the HDAC-VT sample cavity is equal to or less than 2 DEG3And Th4The metal gasket is stable when the temperature is the same or the phase difference is less than or equal to 2 ℃, and the obtained Ttr4Namely the actual phase transition temperature Ttr, and then the corresponding quartz alpha-beta phase transition pressure Ptr is obtained according to an IAPWS-95 pure water multi-parameter state equation. After that, the HDAC pressurizing screw is tightened to compress the volume of the HDAC sample chamber, and then the above experimental operation steps are repeated to obtain the phase transition temperature data of quartz under higher pressure. The quartz α - β transformation temperature Ttr and the corresponding quartz α - β transformation pressure Ptr under different pressure conditions can be obtained by repeating the cycle experiment (the specific results are shown in table 1).
Table 1:
Figure BDA0003175696520000071
Figure BDA0003175696520000081
as can be seen from FIG. 3, when the alpha-beta transus temperature Ttr of quartz is measured under high pressure, the temperature increases, and the quartz is 128cm-1The change frequency of the Raman peak is always higher than that of quartz at 464cm-1The frequency of change of the raman peak.
As can be seen from FIG. 4, the quartz is at 128cm after the temperature is increased to the range of 695--1The frequency variation of Raman peak is much higher than that at 464cm-1The Raman peak frequency changes, so that the quartz is at 128cm-1The crystal alpha-beta phase transition temperature Ttr obtained by the relationship of the Raman peak frequency shift with the temperature change is more accurate.
Example 3
Performing regression analysis according to a series of different quartz alpha-beta phase transition temperatures Ttr and corresponding quartz alpha-beta phase transition pressures Ptr obtained in the steps 1 and 2 to obtain a quartz alpha-beta phase transition P-T relation, which is expressed as follows:
Ptr(±5.6MPa)＝0.0008·Ttr2+2.8056·Ttr-1877.5。
it should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (5)

1. A method for determining the P-T relation of the alpha-beta phase transformation of quartz is characterized by comprising the following steps:
obtaining the quartz alpha-beta phase transition temperature Ttr and the corresponding quartz alpha-beta phase transition pressure Ptr;
determining the quartz alpha-beta phase transition P-T relation according to the quartz alpha-beta phase transition temperature Ttr and the corresponding quartz alpha-beta phase transition pressure Ptr, and expressing as follows:
Ptr(±5.6MPa)＝0.0008·Ttr2+2.8056·Ttr-1877.5；
wherein the alpha-beta phase transition temperature Ttr of the quartz is that the quartz is 128cm-1The temperature when the characteristic peak of the Raman peak position reaches stability is not less than 574 ℃ and not more than 889 ℃;
the method for obtaining the quartz alpha-beta phase transition temperature Ttr and the corresponding quartz alpha-beta phase transition pressure Ptr comprises the following steps (1) or (2):
step (1), when the phase transition pressure Ptr of the quartz alpha-beta is 0.1MPa,
putting a quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, wherein the sample cavity is not required to be sealed, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer, starting heating, and observing that the quartz sample is 128cm in the heating process-1Continuously shifting the characteristic peak of the Raman peak position to the direction with small wave number, and recording the temperature when the characteristic peak is not continuously shifted to the direction with small wave number as the quartz alpha-beta phase transition temperature Ttr;
step (2), when the phase transition pressure Ptr of the quartz alpha-beta is more than 0.1MPa,
s1, putting the deionized water and the quartz sample into a sample cavity of a hydrothermal diamond pressure cavity, and sealing the sample cavity;
s2, connecting the hydrothermal diamond pressure cavity with a laser Raman spectrometer; heating, and recording the disappearance temperature Th of bubbles in the sample cavity1Meanwhile, the quartz sample is observed to be 128cm in the temperature rising process-1The characteristic peak of the Raman peak position is shifted continuously in the direction of small wave number, and the temperature Ttr at which the characteristic peak is not shifted continuously in the direction of small wave number is recorded1；
S3, pausing the temperature rise and slowly reducing the temperature, when bubbles in the sample cavity are observed to reappear, slowly raising the temperature again and recording the disappearance temperature Th of the reappeared bubbles2Meanwhile, the quartz sample is observed to be 128cm in the temperature rising process-1The characteristic peak of the Raman peak position is shifted continuously in the direction of small wave number, and the temperature Ttr when the characteristic peak is not shifted continuously in the direction of small wave number is recorded2；
S4, comparing the bubble disappearance temperature Th1And bubble disappearance temperature Th2And carrying out the following steps a and b;
a. when bubble disappearance temperature Th1And bubble disappearance temperature Th2The same or different by less than or equal to 2 ℃, the temperature Ttr2Namely the quartz alpha-beta phase transition temperature Ttr; then obtaining corresponding quartz alpha-beta phase transition pressure Ptr according to an IAPWS-95 pure water multi-parameter state equation;
b. when bubble disappearance temperature Th1And disappearance of bubblesTemperature Th2The difference is greater than 2 deg.C, steps S1-S4 are repeated.
2. The method for determining according to claim 1, wherein the quartz α - β transformation temperature Ttr is determined by hydrothermal diamond compact coupled with laser raman spectroscopy.
3. A method of determining according to claim 2, characterised in that the hydrothermal diamond pressure chamber is a basett type hydrothermal diamond pressure chamber; the laser Raman spectrometer is a micro confocal Raman spectrometer.
4. The method according to claim 1, wherein the step (1) or step (2) S2 or step (2) S3 warming process specifically comprises the steps of:
in the temperature range from room temperature to 300 ℃, the heating rate of 20-30 ℃/min is adopted; in the temperature range of 300 ℃ and 500 ℃, the heating rate of 10-15 ℃/min is adopted; the temperature rise rate of 5-8 ℃/min is adopted above 500 ℃, and the temperature rise rate is 1-4 ℃/min when the temperature rises to the alpha-beta transformation point of quartz.
5. The method for determining according to claim 1, wherein before the hydrothermal diamond pressure chamber of step (1) or step (2) is connected to the laser Raman spectrometer, the method further comprises performing a linear calibration of the laser Raman spectrometer.
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