Multifunctional integrated chromatographic analysis device

Abstract

The utility model provides a multifunctional integrated chromatographic analysis device. The multifunctional integrated chromatographic analysis device comprises a sample injection unit, a chromatographic analysis unit and a control unit, wherein the sample injection unit is used for sample injection of probe molecules; the separation unit comprises a capillary column and a temperature control box, and the input end of the capillary column is connected with the output end of the sample introduction unit through a first switching valve; the testing unit comprises a three-way valve, a plurality of sample columns and at least one reference column; the carrier gas unit comprises a carrier gas pipeline and a carrier gas interface, one end of the carrier gas pipeline is connected with the carrier gas interface, and the other end is connected with the output end of the capillary column; the detection unit comprises a first detector and a second detector which are respectively connected with the sample outlet ends of the sample column and the reference column. The analysis device disclosed by the utility model is convenient, simple and efficient to use, can be used for gas chromatography and multi-channel surface energy analysis, and can integrate multi-probe separation and multi-channel surface energy analysis, so that the use flexibility of the analysis device is greatly improved, the test range is expanded, the test process is greatly shortened, and the test efficiency is improved.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the surface energy measurement technical field of non-volatile material, especially, relate to a multifunctional integrated chromatographic analysis device. BACKGROUND

[0004]

[0002] In the field of material science and chemical engineering, accurate measurement of the surface energy and thermodynamic properties of solid materials is crucial for understanding and optimizing the performance of materials. Traditional surface energy measurement methods, such as contact angle measurement and surface tension analysis, while providing valuable information, are often limited to the study of less volatile or non-volatile materials, especially high molecular weight polymers, drugs, surfactants, etc. Due to their low volatility, it is difficult to analyze the surface energy of these materials by traditional methods.

[0003] In addition, there are many traditional methods for characterizing the performance of solid surfaces, such as atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, ultraviolet-visible spectroscopy, thermal gravimetric analysis, specific surface area, and porosity analysis. However, these measurement methods can only provide limited information and cannot fully characterize the surface properties of solids; some techniques often require special treatment of materials or measurement under specific conditions (high vacuum or specific temperature), limiting their application range; some methods may not be able to distinguish between surface and internal properties, or accurately characterize the properties of surface micro-regions; some testing methods are time-consuming and have high equipment costs, which are not conducive to large-scale applications; for solids with complex surface chemical components or non-uniform surface structures, traditional methods may not be able to accurately characterize them, greatly limiting their application range.

[0004] Therefore, it is necessary to provide an improved technical solution to address the above-mentioned deficiencies of the prior art. SUMMARY

[0005] In view of the above-mentioned deficiencies of the prior art, the purpose of the present utility model is to provide a multifunctional integrated chromatographic analysis device to solve the problems existing in the prior art when characterizing the surface properties of solids.

[0006] To achieve the above-mentioned purposes and other related purposes, the utility model provides a multifunctional integrated chromatographic analysis device, which comprises:

[0007] A sample injection unit for single probe molecule or mixed probe molecule injection;

[0008] A separation unit comprising a capillary column and a temperature control box arranged outside the capillary column, the input end of the capillary column being connected to the output end of the sample injection unit through a first switching valve, the probe molecules being injected into the capillary column, the temperature control box being used to regulate the temperature of the capillary column, thereby realizing the separation of the probe molecules;

[0009] a testing unit, the testing unit comprising a three-way valve, a plurality of sample columns and at least one reference column, an inlet of the three-way valve being connected with an output end of the capillary column through a second switching valve, one outlet of the three-way valve being connected with input ends of the plurality of sample columns through a first pipeline, another outlet of the three-way valve being connected with an input end of the reference column through a second pipeline, the probe molecules separated from the capillary column being respectively injected into the sample columns and the reference column;

[0010] a carrier gas unit, the carrier gas unit comprising a carrier gas pipeline and a carrier gas interface, one end of the carrier gas pipeline being connected with the carrier gas interface, and the other end being connected with an output end of the capillary column, the carrier gas flowing out of the carrier gas interface carrying the probe molecules for injection;

[0011] a detection unit, the detection unit comprising a first detector and a second detector, the first detector being connected with an output end of the sample column, for identifying and responding to the probe molecules separated from the sample column, the second detector being connected with an output end of the reference column, for identifying and responding to the probe molecules separated from the reference column.

[0012] Preferably, the injection unit comprises a plurality of groups of sample bottles and a total injection pipeline, the output ends of the sample bottles in each group being in communication with the total injection pipeline, the total injection pipeline being connected with an inlet of the first switching valve, and the outlet of the first switching valve being connected with the input end of the capillary column and the inlet of the three-way valve through pipelines respectively.

[0013] Preferably, the injection unit further comprises a sample tank, and the sample bottles in the plurality of groups are accommodated in the sample tank, and a temperature control assembly is arranged on the sample tank, the temperature control assembly being used for temperature adjustment of the sample bottles.

[0014] Preferably, an inlet of the second switching valve is connected with an output end of the capillary column, one outlet of the second switching valve is connected with the inlet of the three-way valve, and another outlet of the second switching valve is further connected with the second detector, and the outlets of the second switching valve are switched, so that the probe molecules separated from the capillary column enter the testing unit or directly enter the second detector.

[0015] Preferably, the number of the sample columns is consistent with the number of the reference columns, and the sample columns and the reference columns are arranged in one-to-one correspondence, the sample columns are used for loading the samples to be tested, and the reference columns are used for loading fillers having no effect on the probe molecules.

[0016] Preferably, the sample end of each sample column is connected with the first pipeline through a first control valve, and the probe molecules are injected into the sample column by switching the interface of the first control valve; the sample end of each sample column is connected with the first detector through a second control valve, and the probe molecules separated by each sample column enter the first detector by switching the interface of the second control valve.

[0017] Preferably, the sample end of each reference column is connected with the second pipeline through a third control valve, and the probe molecules are injected into the reference column by switching the interface of the third control valve; the sample end of each reference column is connected with the second detector through a fourth control valve, and the probe molecules separated by each reference column enter the second detector by switching the interface of the fourth control valve.

[0018] Preferably, the carrier gas pipeline is further provided with a flow control system, and the flow control system comprises one of an electronic pressure control system, an automatic flow control system, an electronic flow control system and a programmed pressure control system.

[0019] Preferably, the first detector and the second detector are both flame ionization detectors or thermal conductivity detectors.

[0020] Preferably, the analysis device further comprises a tail gas path connected with the sample end of the first detector and the sample end of the second detector.

[0021] The utility model also provides a kind of multifunctional integrated chromatographic analysis method, and the analysis method uses above-mentioned multifunctional integrated chromatographic analysis device to test the surface performance of to-be-measured sample.

[0022] As described above, the multifunctional integrated chromatographic analysis device of the utility model has the following beneficial effects:

[0023] The utility model provides a convenient, simple, efficient multifunctional integrated chromatographic analysis device, and the analysis device includes sample introduction unit, separation unit, test unit, carrier gas unit and detection unit, the sample introduction unit includes multiple groups of sample introduction bottles, can continuously sample simultaneously, the setting of capillary column in the separation unit can realize the separation of mixed probe molecules, realizes the test of multiple mixed probes once, expands the test range, greatly shortens the test process, improves test efficiency, after the programmed temperature separation of mixed probes in the capillary column, the carrier gas flow is controlled through the carrier gas unit to make it pass through the sample column and reference column simultaneously, the relative retention time of probe molecules passing through the materials in the sample column and reference column is determined by investigating the peak time of probe molecules on two detectors, the interaction between different probe molecules and the sample to be measured and the surface performance of the sample to be measured are tested through analog calculation combined with multiple parameters, and the accuracy and reliability of the determination result are improved.

[0024] Meanwhile, by switching the outlets of the first switching valve and the second switching valve, the analysis device is equivalent to three devices, which are integrated into one, can be used as a general gas chromatograph, a multi-channel surface energy analyzer, and can also be used as an analysis device integrating multi-probe separation and multi-channel surface energy analyzer, greatly increasing the use flexibility of the analysis device, and realizing comprehensive testing of the thermodynamic performance and physical and chemical performance of non-volatile material surface, such as surface adsorption enthalpy, surface acidity and alkalinity, surface compatibility, diffusion coefficient of probe molecules in adsorbent, various crystallization parameters, difference of surface chemical properties of different batches of samples, determination of surface heterogeneity of single component or multi-component mixture, determination of glass transition temperature of block objects, etc.

[0025] In the utility model, multiple sample columns and reference columns are arranged, which greatly improves the sample testing efficiency, and when the testing of one sample column is completed, the other sample column and the corresponding reference column can be continuously tested by switching the control valve, realizing continuous operation of mixed probe molecules; different samples to be measured are filled in the multiple sample columns, and continuous testing of multiple samples can also be realized, which significantly improves the determination efficiency; in addition, the tail blow gas path is arranged to ensure the peak shape of the probe molecules, so that accurate test results are obtained. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The structure diagram of the multifunctional integrated chromatographic analysis device in the embodiment of the utility model is shown.

[0027] REFERENCE SIGNS

[0028] 11 sample bottle

[0029] 12 total sample introduction pipeline

[0030] 13 sample tank

[0031] 21 temperature-controlled box

[0032] 22 capillary column

[0033] 23 first switching valve

[0034] 31 sample column

[0035] 311 first control valve

[0036] 312 second control valve

[0037] 32 reference column

[0038] 321 third control valve

[0039] 322 fourth control valve

[0040] 33 three-way valve

[0041] 331 first line

[0042] 332 second line

[0043] 34 second switching valve

[0044] 41 carrier gas line

[0045] 42 carrier gas interface

[0046] 51 first detector

[0047] 52 second detector

[0048] 53 tail gas line DETAILED DESCRIPTION

[0049] The embodiments of the present application will be described in detail with specific reference to certain specific embodiments thereof but it is understood that no limitation of the scope of the application is intended. The present application can be implemented or carried out in other ways than those specifically described herein without departing from the spirit and essential characteristics of the application. The present application is thus not limited to the specific embodiments described herein, but covers all modifications and variations falling within the scope of the application.

[0050] Before further description of the present application, it is understood that the present application is not limited in scope to the specific embodiments described herein; and that the embodiments of the present application are used to describe the present application and not to limit the scope of the present application. Unless otherwise indicated, the test methods for the following examples were conducted according to conventional procedures or according to the manufacturer's instructions.

[0051] When the embodiments give numerical ranges, it should be understood that unless the present invention indicates otherwise, each numerical range's two endpoints and any number between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, devices, materials used in the embodiments, any method, device and material of the prior art similar or equivalent to the method, device and material described in the embodiments of the present invention can also be used to implement the present invention according to the mastery of the prior art by those skilled in the art and the description of the present invention.

[0052] Please refer to Figure 1 It should be noted that the drawings provided in the embodiments only illustrate the basic concept of the present invention in a schematic manner, and the drawings only show the components related to the present invention, not the number, shape and size of the components when actually implemented. The actual implementation of each component can be arbitrarily changed, and the component layout pattern can be more complex.

[0053] The present invention provides a multifunctional integrated chromatographic analysis device, which comprises a sample injection unit, a separation unit, a test unit, a carrier gas unit and a detection unit. The sample injection unit is used for the injection of single probe molecules or mixed probe molecules. The separation unit comprises a capillary column 22 and a temperature control box 21 arranged outside the capillary column 22. The input end of the capillary column 22 is connected to the output end of the sample injection unit through a first switching valve 23. The probe molecules are injected into the capillary column 22. The temperature control box 21 is used to control the temperature of the capillary column 22, thereby realizing the separation of the probe molecules. The test unit comprises a three-way valve 33, a plurality of sample columns 31 and at least one reference column 32. The inlet of the three-way valve 33 is connected to the output end of the capillary column 22 through a second switching valve 34. One outlet of the three-way valve 33 is connected to the input end of the plurality of sample columns 31 through a first pipe 331. The other outlet of the three-way valve 33 is connected to the input end of the reference column 32 through a second pipe 332. The separated probe molecules from the capillary column 22 are injected into the sample columns 31 and the reference column 32 through the sample outlet pipe 222. The carrier gas unit comprises a carrier gas interface 42 and a carrier gas pipe 41. One end of the carrier gas pipe 41 is connected to the carrier gas interface 42, and the other end is connected to the output end of the capillary column 22. The carrier gas flowing out of the carrier gas interface 42 carries the probe molecules for injection. The detection unit comprises a first detector 51 and a second detector 52. The first detector 51 is connected to the sample outlet end of the sample column 31, and is used for identifying and responding to the separated probe molecules in the sample column 31. The second detector 52 is connected to the sample outlet end of the reference column 32, and is used for identifying and responding to the separated probe molecules in the reference column 32.

[0054] Specifically, the analysis device in the embodiment of the utility model still integrates control system and data acquisition system, control system and sample unit, test unit, carrier gas unit are electrically connected respectively, the signal input end of data acquisition system is connected with first detector 51, second detector 52 respectively, is used for gathering the detection data of first detector 51, second detector 52 and analysis processing;In addition, the setting of capillary column 22 can realize the separation of mixed probe molecule, realizes the test of multiple mixed probes once, expands the test range, greatly shortens the test process, improves the test efficiency;After the programmed temperature separation of mixed probe in capillary column 22, the carrier gas flow is controlled by carrier gas unit to pass through sample column 31 and reference column 32 simultaneously, the relative retention time of probe molecule passing through the material in sample column 31 and reference column 32 is determined by investigating the peak time of probe molecule on two detectors, the interaction between different probe molecules and the sample to be measured and the surface performance of the sample to be measured are tested by analog calculation combined with multiple parameters, which improves the accuracy and reliability of the determination result, simultaneously, by switching the outlet of first switching valve 23 and second switching valve 34, the analysis device is equivalent to three devices, integrated into one, can be used as ordinary gas chromatography, multi-channel surface energy analyzer, also can be used for the analysis device integrating multi-probe separation and multi-channel surface energy analyzer, greatly increases the use flexibility of the analysis device, realizes the comprehensive test of the thermodynamic performance and physical and chemical performance of non-volatile material surface.

[0055] Multiple sample columns 31 and reference columns 32 greatly increase the sample test efficiency, when one sample column 31 test ends, another sample column 31 and the corresponding reference column 32 can be continuously tested by switching the control valve, realizing the continuous operation of mixed probe molecule;Different samples to be measured are filled in multiple sample columns 31, and multiple samples can also be continuously tested, which significantly improves the determination efficiency.

[0056] In the embodiment of the utility model, sample column 31 and reference column 32 are arranged in column box, and temperature control system is arranged on the column box, which is used for controlling the column temperature of sample column 31 and reference column 32 in the column box.

[0057] In the embodiment of the utility model, the temperature control precision of temperature control system reaches 0.1 DEG C, but the specific structure of temperature control system is not limited here.

[0058] As an example, the sample unit includes multiple groups of sample bottles 11 and total sample inlet pipelines 12 arranged in parallel, the output end of each group of sample bottles 11 is in communication with the total sample inlet pipeline 12, the total sample inlet pipeline 12 is connected with the inlet of first switching valve 23, and the outlet of first switching valve 23 is connected with the input end of capillary column 22 and the inlet of three-way valve 33 through pipelines respectively.

[0059] Specifically, when the outlet of the first switching valve 23 is connected with the inlet of the three-way valve 33 through the pipeline, that is, equivalent to a multi-channel surface energy analysis device, the sample is directly injected into the sample column 31 and the reference column 32, and then the separated sample in the sample column 31 and the reference column 32 is identified and responded by the first detector 51 and the second detector 52 respectively.

[0060] Specifically, the sample injection unit can be used for liquid injection or gas injection, greatly expanding the range of probe molecules. In the specific embodiment of the utility model, the probe molecules can include organic substances that can be vaporized at 300 DEG C. The sample injection unit can include one or a combination of headspace injection, vapor pressure injection, valve injection, liquid injection, and multi-position automatic injector injection.

[0061] As an example, the sample injection unit further includes a sample tank 13, and a plurality of sample bottles 11 are accommodated in the sample tank 13. A temperature control assembly is arranged on the sample tank 13, and the temperature control assembly is used for temperature adjustment of the sample bottles 11.

[0062] Specifically, the sample injection unit can be used for multi-sample injection, and different samples can be continuously tested at the same time. The temperature control assembly on the sample tank 13 warms the sample in the sample bottle 11. When sampling, the sample in the sample bottle 11 or the sample vapor in the sample bottle 11 can be used. The sample bottle 11 is heated by the temperature control assembly, so that the solvent molecules form vapor in the sample bottle 11, which is convenient for micro-control of the sample injection amount. Preferably, the number of sample bottles 11 is 1-20.

[0063] As an example, the inlet of the second switching valve 34 is connected with the output end of the capillary column 22, one outlet of the second switching valve 34 is connected with the inlet of the three-way valve 33, and the other outlet of the second switching valve 34 is further connected with the second detector 52. The probe molecules separated from the capillary column 22 enter the test unit or directly enter the second detector 52 by switching the outlet of the second switching valve 34.

[0064] Specifically, when the outlet of the second switching valve 34 is connected with the three-way valve 33, the analysis device in the specific embodiment of the utility model is equivalent to a device integrating multi-probe separation and multi-channel surface energy analysis. The probe molecules separated from the capillary column 22 are injected into the sample column 31 and the reference column 32 respectively. When the outlet of the second switching valve 34 is connected with the second detector 52, the analysis device in the specific embodiment of the utility model is equivalent to a general gas chromatograph device. The probe molecules separated from the capillary column 22 directly enter the second detector 52 for identification and response.

[0065] For example, the number of sample columns 31 is consistent with the number of reference columns 32, and the sample columns 31 and the reference columns 32 are arranged one by one, the sample columns 31 are used to fill the samples to be tested, and the reference columns 32 are used to fill the fillers which have no effect on the probe molecules.

[0066] Specifically, the same or different samples to be tested can be filled in each sample column 31, and the samples to be tested are non-volatile materials which are stable in surface performance in the range of room temperature to 300 DEG C and can meet the filling requirements, including homopolymers and block copolymers, hyperbranched and dendritic structures, cellulose, fillers and pigments, spices, varnishes and adhesives, inorganic materials such as minerals, food, packaging materials, paints, drugs and surfactants, nanoparticles and nanosheets, building materials, cosmetics, natural and synthetic fibers, supported catalysts and various types of solid materials such as porous, membranes, adsorbents; the filler in the reference column 32 is preferably glass beads.

[0067] Preferably, the sample column 31 is provided with 2-12 (such as 2, 4, 6, 8, 10, 12) sample columns, and the reference column 32 is provided with 2-12 (such as 2, 4, 6, 8, 10, 12) reference columns.

[0068] In addition, in the specific embodiment of the utility model, the length of the sample column 31 is 5cm-60cm (such as 5cm, 10cm, 20cm, 30cm, 40cm, 50cm, 60cm etc.), and the inner diameter of the sample column 31 is 5mm-60mm (such as 5mm, 10mm, 20mm, 30mm, 40mm, 50mm, 60mm etc.).

[0069] For example, the sample end of each sample column 31 is connected with the first pipeline 331 through the first control valve 311, the probe molecules are injected into the sample column 31 by switching the interface of the first control valve 311, the sample end of each sample column 31 is connected with the first detector 51 through the second control valve 312, and the probe molecules separated from each sample column 31 enter the first detector 51 by switching the interface of the second control valve 312.

[0070] For example, the sample end of each sample column 31 is connected with the first pipeline 331 through the first control valve 311, the probe molecules are injected into the sample column 31 by switching the interface of the first control valve 311, the sample end of each sample column 31 is connected with the first detector 51 through the second control valve 312, and the probe molecules separated from each sample column 31 enter the first detector 51 by switching the interface of the second control valve 312.

[0071] Specifically, after the test of one sample column 31 is completed, another sample column 31 and the corresponding reference column 32 can be tested continuously by switching the control valve, thereby realizing continuous operation of the mixed probe molecules; multiple sample columns 31 are respectively filled with different samples to be tested, and continuous testing of multiple samples can also be realized, which significantly improves the measurement efficiency.

[0072] As an example, the carrier gas pipeline 41 is further provided with a flow control system, which includes one of an electronic pressure control system, an automatic flow control system, an electronic flow control system, and a programmed pressure control system.

[0073] Specifically, the purpose of introducing the carrier gas is to carry the probe molecules through each pipeline, the sample column 31, the reference column 32, and finally flow into the first detector 51 and the second detector 52. The flow control system is used to control the flow rate and flow velocity of the carrier gas.

[0074] As an example, the first detector 51 and the second detector 52 are both flame ionization detectors (FID) or thermal conductivity detectors (TCD).

[0075] Specifically, when an FID detector is used, the carrier gas introduced into the carrier gas unit is nitrogen; when a TCD detector is used, the carrier gas introduced into the carrier gas unit is hydrogen or helium.

[0076] As an example, the analysis device further includes a tail gas line 53 , which is connected to the injection end of the first detector 51 and the injection end of the second detector 52 , respectively.

[0077] Specifically, the tail gas path 53 is provided to ensure the peak shape of the probe molecule and to ensure that the first detector 51 and the second detector 52 operate at a high sensitivity.

[0078] The utility model also provides a multifunctional integrated chromatography analysis method, which adopts the above-mentioned Figure 1 The multifunctional integrated chromatography analysis device shown is used to test the surface properties of the sample to be tested.

[0079] Specifically, the above Figure 1 The multifunctional integrated chromatography analysis device shown in the figure tests the surface properties of the sample to be tested. When the outlet of the first switching valve 23 is connected to the input end of the capillary column 22, and the outlet of the second switching valve 34 is connected to the inlet of the three-way valve 33, the following steps are specifically included:

[0080] S1. Pre-load the sample to be tested into each sample column 31, and correspondingly load the reference column 32 with a filler of the same particle size as the sample to be tested that has no force on the probe molecules;

[0081] S2. The mixed probe molecules are injected into the capillary column 22 using the injection unit. When the capillary column 22 is programmed to be heated, the probe molecules are vaporized and separated. At the same time, a carrier gas unit is used to introduce a carrier gas into the output end of the capillary column 22. The carrier gas carries a portion of the probe molecules and flows through the inlet of the three-way valve 33, the outlet of the three-way valve 33, and the first pipeline 331 in sequence. The carrier gas is then diverted to each sample column 31 through the first switching valve. The carrier gas carries another portion of the probe molecules and flows through the inlet of the three-way valve 33, the outlet of the three-way valve 33, and the first pipeline 331 in sequence. The carrier gas is then diverted to each reference column 32 through the third switching valve.

[0082] S3, the sample separated from the sample column 31 enters the first detector 51, and the sample separated from the reference column 32 enters the second detector 52;

[0083] S4. Examining the difference in the peak emission time of the probe molecule on the first detector 51 and the second detector 52 to determine the relative retention time of the probe molecule passing through the reference column 32 and the sample column 31, and combining the mass of the sample to be tested, the pressure at the carrier gas inlet and outlet, the carrier gas flow rate and the column temperature, to obtain the interaction between the probe molecule and the sample to be tested and the surface properties of the sample to be tested through simulation calculation;

[0084] S5. After the test of one sample column 31 is completed, the first switching valve and the third switching valve are switched to detect the sample in another sample column 31 and the corresponding reference column 32, that is, repeat steps S3 and S4.

[0085] When the outlet of the first switching valve 23 is connected to the input end of the capillary column 22, and the outlet of the second switching valve 34 is connected to the second detector 52, the multifunctional integrated chromatographic analysis method in the specific embodiment of the present invention includes the following steps: using the injection unit to inject the mixed probe molecules into the capillary column 22, and when the capillary column 22 is programmed to heat, the probe molecules are vaporized and separated, and at the same time, a carrier gas unit is used to introduce carrier gas into the output end of the capillary column 22, and the carrier gas carries the probe molecules separated from the capillary column 22 into the second detector 52 for identification and response.

[0086] When the outlet of the first switching valve 23 is connected to the inlet of the three-way valve 33, the multifunctional integrated chromatography analysis method in the specific embodiment of the present invention includes the following steps:

[0087] The sample to be tested is pre-loaded into each sample column 31, and the reference column 32 is correspondingly loaded with a filler with the same particle size as the sample to be tested and having no force on the probe molecules;

[0088] The injection unit directly injects the sample into the sample column 31 and the reference column 32 through the three-way valve 33;

[0089] The sample separated from the sample column 31 enters the first detector 51, and the sample separated from the reference column 32 enters the second detector 52;

[0090] The peak time difference of the probe molecules on the first detector 51 and the second detector 52 is observed to determine the relative retention time of the probe molecules passing through the reference column 32 and the sample column 31, and the mass of the sample to be detected, the pressure at the inlet and outlet of the carrier gas, the flow rate of the carrier gas, and the column temperature are combined to obtain the interaction between the probe molecules and the sample to be detected and the surface properties of the sample to be detected through simulation calculation.

[0091] The analysis device is used for determining the thermodynamic properties and physical and chemical properties of non-volatile materials, including homopolymers and block copolymers, hyperbranched and dendritic structures, drugs and surfactants, varnishes and adhesives, nanoparticles and nanosheets, ionic liquids and molten salts, and other various structural composites. Its application fields include polymers, paper and other cellulose, fillers and pigments, flavors, inorganic minerals, food, packaging materials, coatings, drugs, building materials, cosmetics, natural and synthetic fibers, supported catalysts, and microporous materials.

[0092] In order to better understand the multifunctional integrated chromatographic analysis device and analysis method in the utility model, the multifunctional integrated chromatographic analysis device and analysis method in the utility model will be described below with reference to specific embodiments. It should be noted that these embodiments are only descriptive and do not limit the utility model in any way.

[0093] Example 1

[0094] The embodiment provides a multifunctional integrated surface property testing method, which adopts a multifunctional integrated chromatographic analysis device, measures the retention volume of each probe molecule on the surface of a sample A to be detected to study the surface free energy of the sample to be detected, and obtains the adsorption performance of the sample A to be detected to each probe molecule.

[0095] First, referring to Figure 1 , a multifunctional integrated chromatographic analysis device is provided, which includes a sample injection unit, a separation unit, a testing unit, a carrier gas unit, a tail gas path 53 and a detection unit;

[0096] The sample injection unit includes three sample bottles 11 and a total sample injection pipeline 12 arranged in parallel, the output end of each group of sample bottles 11 is in communication with the total sample injection pipeline 12, the total sample injection pipeline 12 is connected with the inlet of the first switching valve 23, the outlet of the first switching valve 23 is connected with the input end of the capillary column 22, and the sample injection unit is used for injecting mixed probe molecules (n-hexane, butanone and toluene as probe molecules). The injection amount of the probe molecules is 0.1 μL, the injection port split ratio of the liquid injection is 10:1, and the injection port temperature is 250℃.

[0097] The separation unit comprises a capillary column 22 and a temperature control box 21 arranged outside the capillary column 22, an input end of the capillary column 22 is connected with an output end of the sample injection unit through a first switching valve, the probe molecules are injected into the capillary column 22, and the temperature control box 21 is used for regulating the temperature of the capillary column 22, so as to realize the separation of the probe molecules, wherein the capillary column 22 is a non-polar column with an inner diameter of 0.32 mm and a length of 30 m;

[0098] The test unit comprises a three-way valve 33, seven sample columns 31 and seven reference columns 32, an inlet of the three-way valve 33 is connected with an output end of the capillary column 22 through a second switching valve 34, one outlet of the three-way valve 33 is connected with an input end of each sample column 31 through a first pipeline 331, and the other outlet of the three-way valve 33 is connected with an input end of the reference column 32 through a second pipeline 332, the probe molecules separated from the capillary column 22 are injected into the sample column 31 and the reference column 32 through a sample outlet pipeline 222, wherein the sample column 31 has an inner diameter of 6 mm, an outer diameter of 10 mm and a length of 10 cm, the column temperature of the sample column 31 and the reference column 32 is 210℃, the sample column 31 is filled with 150 mg of the sample A to be tested, and the reference column 32 is filled with the same volume of glass beads; the sample inlet end of each sample column 31 is connected with the sample injection pipeline 221 through a first control valve 311, the probe molecules are injected into the sample column 31 by switching the interface of the first control valve 311, the sample outlet end of each sample column 31 is connected with the first detector 51 through a second control valve 312, and the probe molecules separated from the sample column 31 enter the first detector 51 by switching the interface of the second control valve 312; the sample inlet end of each reference column 32 is connected with the sample injection pipeline 221 through a third control valve 321, the probe molecules are injected into the reference column 32 by switching the interface of the third control valve 321, and the sample outlet end of each reference column 32 is connected with the second detector 52 through a fourth control valve 322, the probe molecules separated from the reference column 32 enter the second detector 52 by switching the interface of the fourth control valve 322;

[0099] The carrier gas unit comprises a carrier gas interface 42 and a carrier gas pipeline 41, one end of the carrier gas pipeline 41 is connected with the carrier gas interface 42, the other end is connected with an output end of the capillary column 22, and the probe molecules are injected by the carrier gas flowing out from the carrier gas interface 42; wherein an electronic pressure control system is arranged on the carrier gas pipeline 41, so as to control the flow of the carrier gas to be 25 mL / min;

[0100] A tail blow pipeline 53 is connected with the sample inlet end of the first detector 51 and the sample inlet end of the second detector 52 respectively;

[0101] The detection unit comprises a first detector 51 and a second detector 52, both of which are FID detectors, and both of which have a temperature of 250 DEG C; the first detector 51 is connected to the sample outlet end of the sample column 31, and is used to identify and respond to the probe molecules separated in the sample column 31; and the second detector 52 is connected to the sample outlet end of the reference column 32, and is used to identify and respond to the probe molecules separated in the reference column 32.

[0102] Secondly, the embodiment selects n-hexane, butanone and toluene as the mixed probe molecules to test the adsorption performance of the mixed probe molecules on the surface of the measured non-volatile material; after being separated by the capillary column 22, the mixed probe molecules enter the sample column 31 and the reference column 32 respectively for testing.

[0103] The calculation method of the adsorption free energy AG of the non-volatile material to the probe molecules is as follows:

[0104] AG = -RTInVg + K

[0105] In the formula, AG is the standard adsorption free energy (J / mol); R is the universal gas constant 8.3145 J / (mol·K); T is the absolute temperature (K); and K is related to the amount, surface area and adsorption state of the polymer, and thus is a constant (J / mol) in the same chromatographic column.

[0106] The specific retention volume Vg can be obtained by the following formula:

[0107]

[0108] In the formula, t r , t0 are the retention time and dead time (s) of the probe molecules respectively, so as to calculate At; F is the carrier gas flow rate at the outlet of the chromatographic column (i.e. the outlet of the sample column) (mL / s); m is the mass of the stationary phase (g); T is the environmental temperature (K); Pi and P0 are the pressures at the inlet and outlet of the chromatographic column (i.e. the sample column) (Pa) respectively; and Vg is the specific retention volume (mL / g).

[0109] In the embodiment, the adsorption performance of the sample A to be measured to n-hexane, butanone and toluene is investigated, and the adsorption free energies are -25.1 kJ / mol, -28.2 kJ / mol and -30.5 kJ / mol respectively. From the above results, it can be seen that the non-volatile material A has stronger adsorption performance to toluene.

[0110] Example 2

[0111] The embodiment provides a multifunctional integrated chromatographic analysis method, adopts a multifunctional integrated chromatographic analysis device, measures the retention volume of each probe molecule on the surface of a to-be-detected sample B and a to-be-detected sample C to study the surface free energy of the to-be-detected sample, and obtains the adsorption performance of the to-be-detected samples B and C on each probe molecule.

[0112] Firstly, the embodiment provides a multifunctional integrated chromatographic analysis device, which is different from the analysis device in the embodiment 1 in that the sample injection unit 10 is headspace injection, the temperature is 200 DEG C, the No. 1 sample column 31 is filled with 150 mg of the to-be-detected sample B, the No. 2 sample column 31 is filled with 150 mg of the to-be-detected sample C, the No. 1 reference column 32 and the No. 2 reference column 32 corresponding to the sample column 31 are respectively filled with glass beads with the same particle size and volume as B and C, and the rest is the same as the analysis device in the embodiment 1, which is not described herein again.

[0113] Secondly, the n-hexane, butanone and toluene as mixed probe molecules are first separated through the capillary column 22 and then respectively enter the sample column 31 and the corresponding No. 1 reference column 32 for testing, after the testing of the to-be-detected sample B is completed, the first control valve 311 is switched to the No. 2 sample column 31, the third control valve 321 is switched to the No. 2 reference column 32, and the mixed probe molecules are continuously tested.

[0114] The calculation method of the adsorption free energy △G of the non-volatile material on the probe molecule is the same as that in the embodiment 1, which is not described herein again.

[0115] In the embodiment, the adsorption performance of the to-be-detected sample B on the n-hexane, butanone and toluene is investigated, and the adsorption free energy is respectively -14.2 kJ / mol, -16.5 kJ / mol and -19.6 kJ / mol, that is, the non-volatile material B has stronger adsorption performance on toluene.

[0116] In the embodiment, the adsorption performance of the to-be-detected sample C on the n-hexane, butanone and toluene is investigated, and the adsorption free energy is respectively -21.1 kJ / mol, -23.4 kJ / mol and -22.6 kJ / mol, that is, the non-volatile material C has stronger adsorption performance on butanone.

[0117] Embodiment 3

[0118] The embodiment provides a multifunctional integrated chromatographic analysis method, adopts a multifunctional integrated chromatographic analysis device, and separates mixed probes through a capillary column and tests the content of the mixed probes.

[0119] Firstly, the embodiment provides a multifunctional integrated chromatographic analysis device, which is different from that in the embodiment 1 in that the outlet of the first switching valve 23 in the embodiment communicates with the input end of the capillary column 22, the outlet of the second switching valve 34 communicates with the second detector 52, and the others are the same as those in the embodiment 1, which will not be repeated here.

[0120] Secondly, the mixed probe of acetone, toluene, ethyl acetate and n-hexane is injected into the capillary column 22 through the sample injection unit, the capillary column 22 vaporizes and separates the mixed probe according to the programmed temperature (initial temperature 50℃, temperature rising rate 10℃ / min, highest column temperature 200℃), and at the same time, the carrier gas unit is used to introduce the carrier gas into the output end of the capillary column 22, the probe molecules separated from the capillary column 22 are carried into the second detector 52 by the carrier gas for identification and response; wherein the injection amount is 0.1 μl, the injection port split ratio is 25:1, the injection port temperature is 250℃, and the second detector 52 is an FID detector with a temperature of 250℃.

[0121] After the mixed probe of acetone, toluene, ethyl acetate and n-hexane in the embodiment is separated by the capillary column 22, the content is 3.53%, 7.98%, 52.35% and 35.62% respectively.

[0122] Embodiment 4

[0123] The embodiment provides a multifunctional integrated chromatographic analysis method, which uses a multifunctional integrated chromatographic analysis device to measure the retention volume of each probe molecule on the surface of the sample to be measured at different temperatures to study the surface free energy of the sample to be measured.

[0124] Firstly, the embodiment provides a multifunctional integrated chromatographic analysis device, which is different from that in the embodiment 1 in that the outlet of the first switching valve 23 in the embodiment communicates with the input end of the capillary column 22, the outlet of the second switching valve 34 communicates with the second detector 52, and the others are the same as those in the embodiment 1, which will not be repeated here.

[0125] Secondly, toluene is used as a probe molecule to test its adsorption performance on the surface of the sample material to be measured, toluene enters the sample column 31 containing sample D and the corresponding reference column 32 for testing, after the test of the sample to be measured D is completed, the first control valve 311 is switched to the sample column 31 of the sample to be measured E, the third control valve 321 is switched to the corresponding reference column 32, after the test of the sample to be measured E is completed, the control valve is switched to test the sample to be measured F, and the surface energy test of the series of samples is completed.

[0126] The calculation method of the adsorption free energy △G of the solid material to the probe molecule is the same as that in Example 1, which is not repeated here.

[0127] In this example, the adsorption performance of the measured samples D, E and F to toluene is investigated, and the adsorption free energy is-26.4 kJ / mol, -11.5 kJ / mol and -30.2 kJ / mol, respectively.

[0128] In summary, the utility model provides a kind of chromatographic analysis device and analysis method of convenient, simple, efficient, the analysis device includes sample introduction unit, separation unit, test unit, carrier gas unit and detection unit, sample introduction unit includes multiple groups of sample introduction bottle, can simultaneously continuous sample introduction, the setting of capillary column in separation unit can realize the separation of mixed probe molecule, realize the test of multiple mixed probes once, expand test range, greatly shorten test process, improve test efficiency;Mixed probe is separated after program temperature rising in capillary column, pass through carrier gas unit control carrier gas flow to make it pass through sample column and reference column simultaneously, determine the relative retention time of probe molecule through sample column and reference column material by investigating the peak time of probe molecule on two detectors, by analog calculation combined with multiple parameters, and then the interaction between different probe molecules and to-be-measured sample and the surface performance of to-be-measured sample are tested, improve the accuracy and reliability of determination result;At the same time, by switching the outlet of first switch valve and second switch valve, the analysis device is equivalent to three equipments, integrated into one, can be used as ordinary gas chromatograph, multi-channel surface energy analyzer, also can be used for the analysis device integrated with multi-probe separation and multi-channel surface energy analyzer, greatly increase the use flexibility of the analysis device, realize the comprehensive test of the thermodynamic performance and physical and chemical properties of non-volatile material surface, such as surface adsorption enthalpy, surface acidity and alkalinity, surface compatibility, diffusion coefficient of probe molecule in adsorbent, various crystalline parameters, detect the difference of surface chemical properties of different batches of samples, measure the surface heterogeneity of single component or multi-component mixture, measure the glass transition temperature of block object etc..Multiple sample columns and reference columns are provided in the utility model, which greatly improves the sample testing efficiency, when one sample column testing is finished, another sample column and corresponding reference column can be continuously tested by switching control valve, realize the continuous operation of mixed probe molecule;Different to-be-measured samples are filled in multiple sample columns, and continuous testing of multiple samples can also be realized, which significantly improves the determination efficiency;In addition, the tail blow gas path is provided to ensure the peak shape of probe molecule, so as to obtain accurate test result. Therefore, the utility model effectively overcomes the shortcomings in the prior art and has high industrial utilization value.

[0129] The above embodiments only exemplarily illustrate the principles and effects of the present application, and are not used to limit the present application. Any person skilled in the art can modify or change the above embodiments without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those skilled in the art without departing from the spirit and technical thought disclosed by the present application should be covered by the claims of the present application.

Claims

1. A multifunctional integrated chromatographic analysis device, characterized by comprising: The analysis device comprises: a sample injection unit for injection of a single probe molecule or a mixed probe molecule; a separation unit comprising a capillary column and a temperature control box arranged outside the capillary column, an input end of the capillary column is connected with an output end of the sample injection unit through a first switching valve, the probe molecule is injected into the capillary column, and the temperature control box is used for regulating the temperature of the capillary column, so as to realize separation of the probe molecule; a test unit comprising a three-way valve, a plurality of sample columns and at least one reference column, an inlet of the three-way valve is connected with an output end of the capillary column through a second switching valve, one outlet of the three-way valve is connected with input ends of the plurality of sample columns through a first pipeline, and the other outlet of the three-way valve is connected with an input end of the reference column through a second pipeline, and the probe molecule separated from the capillary column is injected into the sample column and the reference column respectively; a carrier gas unit comprising a carrier gas pipeline and a carrier gas interface, one end of the carrier gas pipeline is connected with the carrier gas interface, and the other end is connected with an output end of the capillary column, and the carrier gas flowing out of the carrier gas interface carries the probe molecule for injection; a detection unit comprising a first detector and a second detector, the first detector is connected with an outlet of the sample column, and is used for identifying and responding to the probe molecule separated from the sample column, and the second detector is connected with an outlet of the reference column, and is used for identifying and responding to the probe molecule separated from the reference column.

2. The multi-functional integrated chromatographic analysis device of claim 1, wherein: The sample injection unit comprises a plurality of groups of sample bottles and a total injection pipeline arranged in parallel, the output end of each group of sample bottles is in communication with the total injection pipeline, the total injection pipeline is connected with the inlet of the first switching valve, and the outlet of the first switching valve is respectively connected with the input end of the capillary column and the inlet of the three-way valve through a pipeline.

3. The multi-functional integrated chromatographic apparatus according to claim 2, wherein: The sample injection unit further comprises a sample tank, a plurality of groups of sample bottles are contained in the sample tank, and a temperature control assembly is arranged on the sample tank, and the temperature control assembly is used for temperature regulation of the sample bottles.

4. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The inlet of the second switching valve is connected with the output end of the capillary column, one outlet of the second switching valve is connected with the inlet of the three-way valve, and the other outlet of the second switching valve is further connected with the second detector, the outlets of the second switching valve are switched, and the probe molecule separated from the capillary column enters the test unit or directly enters the second detector.

5. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The number of the sample columns is consistent with the number of the reference columns, the sample columns and the reference columns are arranged one by one, the sample columns are used for loading the sample to be tested, and the reference columns are used for loading the filler which has no force on the probe molecule.

6. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The sample inlet end of each sample column is connected with the first pipeline through a first control valve, and the probe molecules are injected into the sample column by switching the interface of the first control valve; the sample outlet end of each sample column is connected with the first detector through a second control valve, and the probe molecules separated by each sample column enter the first detector by switching the interface of the second control valve.

7. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The sample inlet end of each reference column is connected with the second pipeline through a third control valve, and the probe molecules are injected into the reference column by switching the interface of the third control valve; the sample outlet end of each reference column is connected with the second detector through a fourth control valve, and the probe molecules separated by each reference column enter the second detector by switching the interface of the fourth control valve.

8. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The carrier gas pipeline is further provided with a flow control system, and the flow control system comprises one of an electronic pressure control system, an automatic flow control system, an electronic flow control system and a programmed pressure control system.

9. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The first detector and the second detector are both flame ionization detectors or thermal conductivity detectors.

10. The multi-functional integrated chromatographic apparatus according to claim 1, wherein: The analysis device further comprises a tail blow gas path connected with the sample inlet end of the first detector and the sample inlet end of the second detector respectively.

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