阅读说明：本技术 一种控温微乳液相图的自动化检测装置及方法 (Automatic detection device and method for temperature-controlled microemulsion phase diagram ) 是由 顾宁 金娟 陈功 马宝财 夏强 于 2021-01-18 设计创作，主要内容包括：本发明公开了一种控温微乳液相图的自动化检测装置及方法,包括样品室,样品室插入相态检测箱中,相态检测箱的顶部设有加液器,内部设有恒温水浴锅和搅拌器,搅拌器位于样品室底部,样品室分别与加液器及恒温水浴锅相连,相态检测箱包括箱体,箱体一侧设有光源,光源与样品室之间设有起偏器,箱体另一侧与起偏器相对应的设有旋转检偏器和光强探测器,光源、起偏器、样品室、旋转检偏器和光强探测器的中心位于同一条轴线上,箱体内与光源所在侧面垂直的侧面上设有散射光检测器,且散射光检测器与样品室的中心连线与上述轴线垂直。本发明通过浊度、电导率和偏振光的有无判断微乳液的相态,减少肉眼观察带来的偶然性,同时节省人力和时间。(The invention discloses an automatic detection device and method for a temperature-controlled microemulsion phase diagram, which comprises a sample chamber, wherein the sample chamber is inserted into a phase detection box, the top of the phase detection box is provided with a liquid filler, the inside of the phase detection box is provided with a constant-temperature water bath and a stirrer, the stirrer is positioned at the bottom of the sample chamber, the sample chamber is respectively connected with the liquid filler and the constant-temperature water bath, the phase detection box comprises a box body, one side of the box body is provided with a light source, a polarizer is arranged between the light source and the sample chamber, the other side of the box body, corresponding to the polarizer, is provided with a rotary polarization analyzer and a light intensity detector, the centers of the light source, the polarizer, the sample chamber, the rotary polarization analyzer and the light intensity detector are positioned on the same axis, a side surface in the box body. The invention judges the phase state of the microemulsion through the turbidity, the conductivity and the existence of polarized light, reduces the contingency brought by visual observation, and simultaneously saves labor and time.)

1. An automatic detection device of a temperature-controlled microemulsion phase diagram is characterized by comprising a liquid filler (1), a constant-temperature water bath (2), a stirrer (3), a sample chamber (4) and a phase detection box (5), wherein the sample chamber (4) is inserted into the phase detection box (5), the liquid filler (1) is arranged at the top of the phase detection box (5), the constant-temperature water bath (2) and the stirrer (3) are arranged in the phase detection box, the stirrer (3) is positioned at the bottom of the sample chamber (4), the sample chamber (4) is respectively connected with the liquid filler (1) and the constant-temperature water bath (2), the phase detection box (5) comprises a box body (6), a light source (7) is arranged at one side of the box body (6), a polarizer (8) is arranged between the light source (7) and the sample chamber (4), a rotary polarization detector (9) and a light intensity detector (10) are arranged at the other side of the box body (6) and correspond to the polarizer (8), the centers of the light source (7), the polarizer (8), the sample chamber (4), the rotary polarization analyzer (9) and the light intensity detector (10) are positioned on the same axis, a scattering light detector (11) is arranged on the side surface, perpendicular to the side surface where the light source (7) is positioned, in the box body (6), and the central connecting line of the scattering light detector (11) and the sample chamber (4) is perpendicular to the axis.

2. The device for the automatic detection of the phase diagram of the temperature-controlled microemulsion according to the claim 1, wherein the sample chamber (4) is provided with a plurality of phase detection windows (15) which are respectively opposite to the polarizer (8), the rotary analyzer (9) and the scattered light detector (11) in the phase detection box (5), wherein the centers of one set of the opposite phase detection windows (15) and the sample chamber (4) are positioned on the same axis, and the central connecting line of the other phase detection window (15) and the sample chamber (4) is vertical to the axis.

3. The device for the automated detection of the phase diagram of a temperature-controlled microemulsion according to claim 1 or 2, characterized in that conductivity meter electrodes (12) are inserted in the sample chamber (4).

4. The automatic detection device for the temperature-controlled microemulsion phase diagram according to claim 3, wherein a circulating water heating jacket (16) is wrapped outside the sample chamber (4), and a water inlet (17) and a water outlet (18) are arranged on the circulating water heating jacket (16) and are respectively connected with the constant-temperature water bath kettle (2).

5. The device for automatically detecting the temperature-controlled microemulsion phase diagram according to claim 4, wherein the sample chamber (4) is provided with a sample inlet (13) and a sample outlet (14), wherein the sample inlet (13) is connected with the liquid charger (1), and the sample inlet (13) and the sample outlet (14) are respectively provided with an electromagnetic valve (19).

6. The automatic detection device for the phase diagram of the temperature-controlled microemulsion according to claim 1, wherein the liquid adding device (1) is a micro-syringe pump or a peristaltic pump, and the liquid adding mode is intermittent liquid adding.

7. The automatic detection device of the phase diagram of the temperature-controlled microemulsion according to claim 1, wherein the light emitted by the light source (7) passes through the polarizer (8), a set of opposite phase detection windows (15), the rotary analyzer (9) and the light intensity detector (10) to detect the polarization phenomenon of the sample.

8. The apparatus for the automated phase diagram detection of temperature-controlled microemulsions according to claims 1 or 7, characterized in that said light source (7) emits light through a set of mutually perpendicular phase detection windows (15) and scattered light detectors (11) to detect the turbidity of the sample.

9. The apparatus for the automated detection of the phase diagram of a temperature-controlled microemulsion according to claim 1, wherein the stirrer (3) is a magnetic stirrer or a mechanical stirrer.

10. An automatic detection method of a temperature-controlled microemulsion phase diagram is characterized by comprising the following steps:

(1) according to composition P_xWeighing a sample and placing the sample in a sample chamber;

(2) opening the constant-temperature water bath kettle and the stirrer, heating the sample to a set temperature T, and mixing the sample;

(3) starting a phase state detection box, and judging the phase state S of the sample by detecting the polarization phenomenon, turbidity and conductivity of the sample₀；

(4) Starting the liquid charger to add liquid to the sample chamber and recording the total accumulated liquid volume V_i；

(5) Detecting the phase S of the sample after liquid adding through a phase detection box_i；

(6) Repeating steps (4) - (5) until no new phase is generated;

(7) automatically cleaning the sample chamber;

(8) changing the sample composition P_xRepeating steps (1) - (7);

(9) closing all switches;

(10) according to the obtained P_x，V_i，S_iFinding phase transition point and plotting phaseFigure (a).

Technical Field

The invention relates to an automatic detection device and method of a phase diagram, in particular to an automatic detection device and method of a temperature control microemulsion phase diagram.

Background

The microemulsion is a homogeneous system consisting of an oil phase, a water phase, an emulsifier and an auxiliary emulsifier, and is a thermodynamically stable nano-dispersion system. Microemulsion technology has been widely used in the fields of daily chemical industry, tertiary oil recovery, material science, enzyme catalysis, etc. Due to the characteristics of small particle size, transparency and the like, the microemulsion is also generally concerned and widely researched in the application of the microemulsion as a fat-soluble drug carrier in the fields of nano-drugs and biomedicine.

According to the thermodynamic theory, energy must be supplied from the outside to convert an oil/water system into an emulsion. The microemulsion is a stable mixing system formed spontaneously by an oil phase, a water phase, an emulsifier and a co-emulsifier in a proper proportion, and the essence and the forming mechanism of the microemulsion are an important research direction of interface science. By changing the amount of the system components, the microemulsion can have different phase states, and the phase states of the microemulsion are mainly divided into the following phases: an oil-in-water nanoemulsion; a water-in-oil nanoemulsion; a bicontinuous nanoemulsion; liquid crystal state and turbid state, the first three are clear states. The phase diagram is the most basic tool for studying microemulsions and describes the correlation between the ratios of the components and the phase states. The detailed phase behavior information of the microemulsion can be obtained through a phase diagram, and the method has important significance for theoretical research and practical application guidance of the microemulsion.

Usually, a phase diagram of the microemulsion is detected by a titration method, namely, water is continuously added into an oil phase containing an emulsifier and a co-emulsifier, and a boundary point is determined by detecting the change of the phase behavior of a system, so that the phase diagram is drawn. In actual detection, simple glass instruments such as test tubes are often used, and the phase behavior of the microemulsion at normal temperature is mainly judged by visual observation. For some special systems, such as nano-emulsion obtained at higher temperature, the system temperature is very important for detecting the liquid phase behavior of the micro-emulsion.

CN1314957C discloses a detection device for drawing a temperature-controlled phase diagram of nano emulsion, which can be used for regulating and controlling the operation temperature in phase diagram detection. However, the phase determination in the detection process is still mainly observed by naked eyes, and the detection steps are complex.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide an automatic detection device and method for a temperature-controlled microemulsion phase diagram, which are used for improving the detection accuracy and the automatic mechanization degree of the phase diagram and improving the detection efficiency.

The technical scheme is as follows: the invention comprises a liquid filler, a constant temperature water bath, a stirrer, a sample chamber and a phase detection box, wherein the sample chamber is inserted into the phase detection box, the top of the phase state detection box is provided with a liquid filler, the interior of the phase state detection box is provided with a constant temperature water bath kettle and a stirrer, the stirrer is positioned at the bottom of the sample chamber, the sample chamber is respectively connected with the liquid filler and the constant temperature water bath, the phase state detection box comprises a box body, one side of the box body is provided with a light source, a polarizer is arranged between the light source and the sample chamber, the other side of the box body is provided with a rotary polarization analyzer and a light intensity detector corresponding to the polarizer, the centers of the light source, the polarizer, the sample chamber, the rotary polarization analyzer and the light intensity detector are positioned on the same axis, a scattered light detector is arranged on the side surface in the box body, which is vertical to the side surface of the light source, and the central connecting line of the scattered light detector and the sample chamber is vertical to the axis.

The sample chamber is provided with a plurality of phase detection windows which are respectively opposite to a polarizer, a rotary polarization analyzer and a scattered light detector in the phase detection chamber, the centers of one group of opposite phase detection windows and the center of the sample chamber are positioned on the same axis, and the center connecting line of the other phase detection window and the sample chamber is vertical to the axis.

And a conductivity meter electrode is inserted into the sample chamber and can be used for detecting the conductivity of the sample.

The sample room outside parcel have a circulating water heating jacket, the circulating water heating jacket on be equipped with water inlet and delivery port to link to each other with constant temperature water bath respectively, accessible circulating water heating jacket is to the sample temperature control in the sample room.

The sample chamber on be equipped with introduction port and outlet, wherein, introduction port is connected with the liquid charger, introduction port and outlet on be equipped with the solenoid valve respectively.

The liquid adding device is a micro-injection pump or a peristaltic pump, and the liquid adding mode is intermittent liquid adding.

The light emitted by the light source passes through the polarizer, a group of opposite phase state detection windows, the rotary analyzer and the light intensity detector to detect the polarization phenomenon of the sample.

The light emitted by the light source passes through a group of mutually perpendicular phase state detection windows and a scattered light detector to detect the turbidity of the sample.

The stirrer is a magnetic stirrer or a mechanical stirrer and can stir and mix the sample in the sample chamber.

An automatic detection method of a temperature-controlled microemulsion phase diagram comprises the following steps:

(1) according to composition P_xWeighing a sample and placing the sample in a sample chamber;

(2) opening the constant-temperature water bath kettle and the stirrer, heating the sample to a set temperature T, and mixing the sample;

(3) starting a phase state detection box, and judging the phase state S of the sample by detecting the polarization phenomenon, turbidity and conductivity of the sample₀；

(4) Starting the liquid charger to add liquid to the sample chamber and recording the total accumulated liquid volume V_i；

(5) Detecting the phase S of the sample after liquid adding through a phase detection box_i；

(6) Repeating steps (4) - (5) until no new phase is generated;

(7) automatically cleaning the sample chamber;

(8) changing the sample composition P_xRepeating steps (1) - (7);

(9) closing all switches;

(10) according to the obtained P_x，V_i，S_iThe phase transition point is found and the phase diagram is plotted.

Has the advantages that: the invention judges the phase state of the microemulsion through the detection data of turbidity, conductivity and polarized light, can reduce the contingency brought by visual observation, and simultaneously saves manpower and time; automatic liquid adding can be carried out through the liquid adding device, so that the labor is saved; the temperature of the microemulsion can be accurately controlled; the sample chamber can be automatically cleaned and can be repeatedly used, so that the labor and the materials are saved; the accurate sample adding recording is carried out through the liquid adding device, and the phase transition point can be accurately judged by combining the accurate judgment of the phase state, so that the accuracy of the phase diagram is higher.

Drawings

FIG. 1 is a schematic view of the overall structure of the present invention;

FIG. 2 is a schematic diagram of the internal structure of the phase detection box according to the present invention;

FIG. 3 is a schematic diagram of a sample chamber structure according to the present invention.

Detailed Description

The invention will be further explained with reference to the drawings.

As shown in figure 1, the device comprises a liquid adding device 1, a constant-temperature water bath kettle 2, a stirrer 3, a sample chamber 4 and a phase detection box 5, wherein the sample chamber 4 is inserted into the phase detection box 5, the liquid adding device 1 is arranged at the top of the phase detection box 5, the constant-temperature water bath kettle 2 and the stirrer 3 are arranged inside the phase detection box, and the device is higher in overall integration level and integration level. The liquid filler 1 is connected with a sample inlet 13 of the sample chamber 4, the constant temperature water bath 2 is connected with a water inlet 17 and a water outlet 18 of the sample chamber 4, and the stirrer 3 is positioned at the bottom of the sample chamber 4. The stirrer 3 is a magnetic stirrer or a mechanical stirrer and can stir and mix the sample in the sample chamber 4. The liquid charger 1 is used to add liquids, including water, aqueous or organic solutions, to the sample chamber 4. The liquid adding device 1 is a micro-injection pump or a peristaltic pump, the liquid adding mode is intermittent liquid adding, 5-50 microliters of equivalent liquid is added each time, then 5min is waited for phase detection, liquid is added again, and accurate, continuous and automatic liquid adding can be carried out by setting a liquid adding program without manually adding the liquid dropwise.

As shown in fig. 2, the phase detection box 5 includes a box body 6, a light source 7, a polarizer 8, a rotation analyzer 9, a light intensity detector 10, a scattered light detector 11 and a conductivity meter electrode 12, wherein the light source 7 is located on one side surface of the box body 6, the polarizer 8 is arranged between the light source 7 and the sample chamber 4, and the rotation analyzer 9 and the light intensity detector 10 are arranged on the other side of the box body 6 corresponding to the polarizer 8. The centers of the light source 7, the polarizer 8, the sample chamber 4, the rotary analyzer 9 and the light intensity detector 10 are positioned on the same axis, the scattered light detector 11 is positioned on the side surface vertical to the side surface where the light source 7 is positioned in the box body 6, and the central connecting line of the scattered light detector 11 and the sample chamber 4 is vertical to the axis. Conductivity meter electrodes 12 are inserted into the sample chamber 4.

As shown in fig. 3, the sample chamber 4 comprises a sample inlet 13, a sample outlet 14, three phase detection windows 15 and a circulating water heating jacket 16, water can be added through the sample inlet 13, the constant temperature water bath 2 and the stirrer 3 heat and stir the liquid, the sample outlet 14 discharges water, the inner wall of the sample chamber 4 is automatically cleaned, the cleaned sample cell can be reused, the loss of the sample tube is reduced, and the sample inlet 13 and the sample outlet 14 are respectively provided with an electromagnetic valve 19. The three phase detection windows 15 are respectively opposite to the polarizer 8, the rotary analyzer 9 and the scattered light detector 11 in the phase detection box 5, wherein the centers of the two phase detection windows 15 and the center of the sample chamber 4 are on the same axis, and the central connecting line of the third phase detection window 15 and the sample chamber 4 is vertical to the axis. The circulating water heating jacket 16 wraps the outer side of the sample chamber 4, the circulating water heating jacket 16 is connected with the constant-temperature water bath kettle 2, the circulating water heating jacket 16 is provided with a water inlet 17 and a water outlet 18, and the temperature of the sample in the sample chamber 4 can be controlled through the circulating water heating jacket 16.

The light emitted by the light source 7 passes through the polarizer 8, the two opposite phase detection windows 15, the rotary analyzer 9 and the light intensity detector 10, and can be used for detecting the polarization phenomenon of a sample; the light emitted by the light source 7 passes through two mutually perpendicular phase state detection windows 15 and the scattered light detector 11 and can be used for detecting the turbidity of a sample; the conductivity meter electrodes 12 are inserted into the sample chamber 4 and can be used to detect the conductivity of the sample. The phase state of the sample can be judged by detecting the polarization phenomenon, turbidity and conductivity of the sample. In the aspect of data processing and analysis, the data detected by the liquid adding device 1, the light intensity detector 10, the scattered light detector 11 and the conductivity meter can be further connected with a computer through a data acquisition card for data acquisition, display and storage.

The phase detection part of the invention comprises conductivity detection, turbidity detection and polarization phenomenon detection. The sample chamber 4 is provided with three phase detection windows 15 which are respectively opposite to the light source 7, the light intensity detector 10 and the scattered light detector 11, share the same light source 7, and detect the polarization and the turbidity of the sample from two vertical directions. The electrodes of the conductivity meter are inserted into the sample chamber 4 for detecting the turbidity of the sample. The phase state detection system can simultaneously detect the conductivity, polarization phenomenon and turbidity change of the system on line, thereby accurately judging the phase state of the system: a. carrying out quantitative determination on the turbid state and the clear state by using turbidity, and determining the ranges of the microemulsion including oil-in-water type nano emulsion, water-in-oil type nano emulsion and bicontinuous type nano emulsion; b. determining the range of the bicontinuous nanoemulsion by using the change of the conductivity; c. the presence or absence of the polarization phenomenon is used to determine the liquid crystal state. On one hand, the system is analyzed through the quantitative data of the polarized light image, the conductivity and the turbidity, so that the accuracy of phase state judgment is improved, and more detailed surface interface information can be obtained; on the other hand, the phase state is judged through instrument detection, the experiment phenomenon does not need to be continuously observed manually, and the labor is greatly saved while the deviation caused by direct observation of naked eyes is reduced.

The automatic detection method comprises the following steps:

(1) according to composition P_xWeighing a sample and placing the sample in a sample chamber;

(2) opening the constant-temperature water bath kettle and the stirrer, heating the sample to a set temperature T, and mixing the sample;

(3) starting a phase state detection box, and judging the phase state S of the sample by detecting the polarization phenomenon, turbidity and conductivity of the sample₀；

(4) Starting the liquid charger to add liquid to the sample chamber and recording the total accumulated liquid volume V_i；

(5) Detecting the phase S of the sample after liquid adding through a phase detection box_i；

(6) Repeating steps (4) - (5) until no new phase is generated;

(7) automatically cleaning the sample chamber;

(8) changing the sample composition P_xRepeating steps (1) - (7);

(9) closing all switches;

(10) according to the obtained P_x，V_i，S_iThe phase transition point is found and the phase diagram is plotted. The phase diagram drawing method comprises the following steps:

1) taking an equilateral triangle ABC;

2) 10 equal division points P on BC edge_X,X＝1,2,…9；

3) Determining compositions, e.g. P₁The initial proportion is anhydrous, and is B, C is mixed to form CP1/BP1 which is 0.1/0.9, namely C%/B% whichis 1/9;

4) obtaining a series P by an automated detection method of a temperature-controlled microemulsion phase diagram₁，V_i，S_iAccording to S_iFind out the point TP where the phase change occurs₁，V_T，S_TTotal volume V of liquid to be added_TI.e. converted into the percentage Q of each substance_T；

5) According to Q_TDetermining AP₁An upper phase transition point;

6) determining AP according to steps 3) -5)₂-AP₃All the phase change points on;

7) and drawing a phase diagram according to the phase change points.