CN111595885A - Calibration standard sample for testing fluorine content and sealing method and application thereof - Google Patents
Calibration standard sample for testing fluorine content and sealing method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of fluorine content detection, and particularly relates to a calibration standard sample for detecting fluorine content, a sealing method and application thereof. The calibration standard sample provided by the invention comprises a first calibration standard sample and a second calibration standard sample, wherein a liquid fluoropolymer is used as the first calibration standard sample, a solid fluoropolymer is used as the second calibration standard sample, the accuracy of a standard curve obtained by fitting is high, the detection result of the content of fluorine element is more accurate, and the calibration standard sample is stable and reliable and is suitable for nuclear magnetic resonance instruments of different models; the calibration standard sample provided by the invention takes the liquid fluoropolymer as the first calibration standard sample, the performance of the calibrated instrument is stable, the fluorine element signal in the sample can be effectively tested, the test performance is stable, the state of the instrument is better, and the fluorine signal detection result is more accurate.
Description
Technical Field
The invention belongs to the technical field of fluorine content detection, and particularly relates to a calibration standard sample for detecting fluorine content, a sealing method and application thereof.
Background
The rubber is a synthetic elastomer with a main chain or a side chain connected with fluorine atoms with extremely strong electronegativity, wherein the bond energy of carbon-fluorine bonds is very large, the covalent radius of the fluorine atoms is half of the length of the carbon-carbon bonds, and the stability of the carbon-carbon bonds can be effectively protected, so that the rubber has excellent performances which are incomparable with other rubbers, such as oil resistance, acid resistance, good physical and mechanical properties, electric insulation, radiation resistance and the like, is widely applied in the fields of aerospace, automobiles, petroleum, household appliances and the like, and is a key material which cannot be replaced in national defense advanced industry.
According to the GB/T5576, fluororubbers are mainly classified into three main categories, namely FKM, FEPM and FFKM. Wherein FKM represents a fluorine rubber containing a fluorine, perfluoroalkyl or perfluoroalkoxy substituent in the polymer chain, FEPM represents a copolymer of tetrafluoroethylene and propylene, and FFKM represents a perfluoro rubber containing all the substituents of fluorine, perfluoroalkyl or perfluoroalkoxy in the polymer. The fluorine content of the three types of rubber is between 50 and 80 percent, and the fluorine content in the fluororubber is closely related to the mechanical and chemical properties of the fluororubber.
At present, in the national standards of fluororubbers, such as GB/T30308-.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, during fluorine content analysis, an instrument is corrected by taking a solid fluoropolymer as a standard sample, and the corrected instrument is unstable in detecting fluorine element signals, so that the detection of the fluorine element content is inaccurate, and the like, so that the fluorine element content calibration standard sample, and the preparation method and the application thereof are provided.
Therefore, the invention provides the following technical scheme.
The invention provides a calibration standard sample for testing fluorine content, which comprises a first calibration standard sample and a second calibration standard sample;
the first calibration standard comprises a liquid fluoropolymer; the second calibration standard includes a solid fluoropolymer.
The solid fluorine-containing polymer is polytetrafluoroethylene, fluorinated ethylene propylene or polyvinylidene fluoride.
The liquid fluoropolymer is perfluorobenzene or tetrafluoroethylene.
The first and second calibration standards further comprise first and second seals; the first sealing element is made of a fluorine-free polymer, and the fluorine-free polymer is polymethyl methacrylate, polyether ether ketone or polystyrene; the second sealing element is made of fluorine-free plastic.
The invention also provides a sealing method of the calibration standard sample, which comprises the steps of adding the liquid fluoropolymer into a sample bottle, sealing and standing to obtain the first calibration standard sample;
the sealing method of the second calibration standard sample comprises the steps of adding the solid fluoropolymer into a sample bottle, sealing and standing to obtain the second calibration standard sample.
Further, the sealing method of the first calibration standard sample comprises the steps of adding liquid fluoropolymer into a sample bottle, then dropwise adding photosensitive glue on the outer side wall of a first sealing element, screwing the outer side wall into the open end of the sample bottle, dropwise adding photosensitive glue on the top of the first sealing element, covering a second sealing element after light irradiation solidification, and standing to obtain the first calibration standard sample;
adding a solid fluoropolymer into a sample bottle, dripping photosensitive glue on the outer side wall of a first sealing element, screwing the sample bottle into the open end of the sample bottle, dripping photosensitive glue on the top of the first sealing element, irradiating and solidifying, covering a second sealing element, and standing to obtain a second calibration standard sample;
the photosensitive adhesive is prepared from (93-98.8) by mass: (0.2-1): (1-6) the polymer precursor, the auxiliary agent and the initiator; the polymer precursor is a mixture of a monomer and a prepolymer thereof, and the monomer is epoxy acrylate, polyurethane acrylate, polyether acrylate, polyester acrylate or acrylic resin;
the auxiliary agent comprises isobornyl acrylate, hydroxyethyl methacrylate, tripropylene glycol diacrylate or pentaerythritol triacrylate; the auxiliary agent is used for accelerating the curing of the photosensitive adhesive;
the initiator comprises 2-hydroxy-2-methyl-1-phenyl-1-acetone (trade name is 1173 auxiliary agent), 1-hydroxycyclohexyl phenyl ketone (trade name is 184 auxiliary agent) or diphenyl acetone.
The photosensitive adhesive is treated by vacuumizing for 30-120 min.
The distance between the top end of the first sealing element and the top end of the open end of the sample bottle is 1-3 mm; dripping photosensitive glue on the top of the first sealing element to the top end of the open end of the sample bottle;
the mass range of the solid fluoropolymer is 0.1 to 10 g.
The second calibration standard needs to be kept still for more than 24 hours at 25 ℃ before being used.
In addition, the invention also provides an application of the calibration standard sample or the calibration standard sample obtained by the sealing method in fluorine-containing sample detection; the fluorine-containing sample is a solid fluorine-containing polymer and a fluorine signal can be detected by a nuclear magnetic resonance instrument.
Further, the fluorine-containing sample is a fluororubber.
The application comprises that when a calibration standard sample is used for testing the fluorine content of the fluororubber, the first calibration standard sample is used for calibrating a nuclear magnetic resonance instrument; the second calibration standard is used for calibrating a standard curve of the fluorine element content.
When the calibration standard sample is applied, the calibration standard sample needs to be placed in a supporting piece and then tested;
the support is made of a fluorine-free polymer, and the fluorine-free polymer is polymethyl methacrylate, polyether ether ketone or polystyrene.
The technical scheme of the invention has the following advantages:
1. the invention provides a calibration standard sample for testing the content of fluorine, which comprises a first calibration standard sample and a second calibration standard sample, wherein the first calibration standard sample comprises liquid fluoropolymer, and the second calibration standard sample comprises solid fluoropolymer; the method comprises the steps that a liquid fluoropolymer is used as a first calibration standard sample, a solid fluoropolymer is used as a second calibration standard sample, the first calibration standard sample can enable an instrument to lock a fluorine element signal and discharge interference of other signals after a nuclear magnetic resonance instrument is calibrated, compared with the solid fluoropolymer calibration instrument, the frequency change range of the fluorine element signal locked by the instrument after the liquid fluoropolymer calibration is small, the detection result of the fluorine element signal is more accurate, when the fluorine element signal in the second calibration standard sample is detected, the signal amplitude is stable, the signal-to-noise ratio is high, the correlation coefficient of a standard curve obtained through fitting is high, the result of the detection of the content of the fluorine element is more accurate, the sample is stable and reliable, the method can be repeatedly used for a long time, and the method is suitable for nuclear magnetic resonance instruments of different models; the calibration standard sample provided by the invention takes the liquid fluoropolymer as the first calibration standard sample, the performance of the calibrated instrument is stable, the fluorine element signal in the sample can be effectively tested, the test performance is stable, the state of the instrument is better, and the fluorine signal detection result is more accurate.
The calibration standard sample provided by the invention is suitable for measuring the fluororubber with a wider fluorine content range, and has the advantages of wide linear range (the range of positive correlation between nuclear magnetic signals and fluorine content is large, namely the test range is larger) and stronger applicability.
2. According to the calibration standard sample for testing the content of the fluorine element, the signal-to-noise ratio of perfluorobenzene or tetrafluoroethylene in the first calibration standard sample is high, the fluorine signal of the corrected instrument is stable for a long time, the state of the instrument is good, and the detection of the fluorine signal is more accurate; the properties of the polytetrafluoroethylene, the polyfluorinated ethylene propylene or the polyvinylidene fluoride in the second calibration standard sample are similar to those of the fluororubber, so that a standard curve can be formulated, the accuracy of the standard curve obtained by fitting is higher, and the test result of the content of the fluorine element in the fluororubber is more accurate; in addition, polytetrafluoroethylene, polyfluorinated ethylene propylene or polyvinylidene fluoride are not easy to age, have stable properties, can be repeatedly used for a long time, have good sealing performance of the calibration standard sample, are not easy to be polluted, and can detect fluorine element signals in a low-field nuclear magnetic test.
The first sealing piece and the second sealing piece are made of materials without fluorine, so that the influence on the calibration curve of the calibration sample can be eliminated.
3. According to the sealing method of the calibration standard sample provided by the invention, the calibration standard sample prepared by the method has better sealing property, the fitted calibration curve is more accurate, the method is simple to operate and lower in cost, and the prepared calibration standard sample has accurate fluorine content, is stable and reliable, can be repeatedly used for a long time, and is suitable for nuclear magnetic resonance instruments of different models.
The method can completely remove the gas in the photosensitive adhesive by controlling the vacuumizing time of the photosensitive adhesive, and bubbles are not easy to appear in the solidification process, so that the sample bottle has better sealing property; by controlling the distance between the top of the first seal and the top of the open end of the sample bottle, the seal is improved.
The second calibration standard sample is kept still for at least 24 hours at 25 ℃ before being used, so that the solidification effect of the photosensitive adhesive is better, and the sealing performance of the sample bottle is better.
4. The application of the calibration standard sample provided by the invention in the detection of the fluorine-containing sample is characterized in that the first calibration standard sample is used for calibrating a nuclear magnetic resonance instrument, the second calibration standard sample is used for making a standard curve, and then the fluorine content of the fluorine-containing sample is tested; before testing, the calibration standard sample is placed into the support piece and then tested, the application can make a standard curve of the fluorine element, rapid nondestructive testing of the content of the fluorine element is realized, and the testing result is accurate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a first calibration standard in example 1 of the present invention; wherein, 1 is photosensitive glue, 2 is a first sealing member, the structural schematic diagram is shown in figure 3, 3 is perfluorobenzene, 4 is a second sealing member, and 5 is a chromatographic bottle;
FIG. 2 is a schematic structural diagram of a second calibration standard in example 1 of the present invention; wherein, 1 is photosensitive glue, 2 is a first sealing element, the structural schematic diagram is shown in figure 3, 3' is solid fluoropolymer, 4 is a second sealing element, and 5 is a chromatographic bottle;
FIG. 3 is a schematic structural view of a first seal member in embodiment 1 of the present invention;
FIG. 4 is a schematic structural view of a support member in embodiment 1 of the present invention;
FIG. 5 is a NMR signal-quality calibration curve fitted to calibration standards in example 1 of the present invention;
FIG. 6 is a NMR signal-quality calibration curve fitted to calibration standards in example 2 of the present invention;
FIG. 7 is a NMR signal-mass standard curve obtained by fitting a calibration standard of comparative example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In examples 1 and 2, the photosensitive adhesive is a polymer precursor, isobornyl acrylate and 1173 auxiliaries in a mass ratio of 95:1:4, and the polymer precursor is epoxy acrylate and a prepolymer thereof.
Example 1
The embodiment provides a calibration standard sample for testing the content of fluorine element, a preparation method and an application thereof, and concretely comprises the following steps,
the calibration standard sample comprises a first calibration standard sample and a second calibration standard sample; the first calibration standard sample comprises perfluorobenzene, photosensitive glue, a sample bottle, a first sealing element (made of polymethyl methacrylate, and the structural schematic diagram is shown in figure 3) and a second sealing element (made of polyvinyl chloride); wherein, specifically, the sample bottle is a chromatographic bottle;
the second calibration standard sample comprises polytetrafluoroethylene, photosensitive glue, a sample bottle, a first sealing element (made of polymethyl methacrylate, and the structural schematic diagram is shown in figure 3) and a second sealing element (made of polyvinyl chloride); wherein, specifically, the sample bottle is a chromatographic bottle;
the preparation method of the calibration standard sample comprises the following steps,
processing polytetrafluoroethylene into column bodies with the length of 20mm, wherein the column bodies are 5 and are named as P1, P2, P3, P4 and P5 in sequence, and the mass of fluorine elements in the polytetrafluoroethylene is distributed in a gradient manner, which is shown in Table 1; then, processing the polymethyl methacrylate, wherein the processing parameters are as follows: the shape is a truncated cone structure, the diameter DC of the upper bottom is 0.6 plus or minus 0.05cm, the diameter AB of the lower bottom is 0.7 plus or minus 0.05cm, and the height OO10.8 ± 0.05cm, see fig. 3, for a total of 6, which are first seals, noted B1, B2, B3, B4, B5 and B6;
vacuumizing the photosensitive adhesive for 60min, injecting 4ml of perfluorobenzene into a 5ml chromatographic bottle by using an all-glass syringe, dripping the photosensitive adhesive on the side wall of B1, and slightly screwing into the chromatographic bottle to enable the top end of the photosensitive adhesive to be 1mm lower than the top end of the chromatographic bottle; dripping photosensitive adhesive into the chromatographic bottle to the top end of the chromatographic bottle, illuminating for 15min to completely solidify the photosensitive adhesive, screwing a chromatographic bottle cap (a second sealing element), standing for 24h at room temperature to obtain a first calibration standard sample, marking as a calibration standard sample 0, and showing a structural schematic diagram in fig. 1;
respectively placing P1, P2, P3, P4 and P5 into the chromatographic bottles, dripping photosensitive glue on the side walls of B2, B3, B4, B5 and B6, respectively screwing the chromatographic bottles into the chromatographic bottles to enable the top ends of the chromatographic bottles to be 1mm lower than the top ends of the chromatographic bottles, respectively dripping the photosensitive glue into 5 chromatographic bottles, completely solidifying the photosensitive glue by illumination for 15min, screwing down a chromatographic bottle cap (a second sealing element), standing for 24h at room temperature to obtain second calibration samples which are respectively marked as calibration samples 1-5, wherein the structural schematic diagram is shown in FIG. 2;
TABLE 1 quality of Polytetrafluoroethylene and fluorine
| Standard sample number | P1 | P2 | P3 | P4 | P5 |
| Quality of standard sample material (g) | 1 | 1 | 1 | 1 | 1 |
| Mass (g) of fluorine element in standard sample | 0.224 | 0.378 | 0.514 | 0.635 | 0.719 |
The application of the first calibration standard sample and the second calibration standard sample, which are used for testing the fluorine element content of the fluororubber, specifically comprises the following steps,
after a chromatographic bottle cap of a calibration standard sample 0 is removed, the chromatographic bottle cap is placed into a support piece, the bottom of the support piece is provided with a threaded structure and is in threaded connection with the bottle mouth of a chromatographic bottle, the structure of the support piece is shown in figure 4, then the support piece is placed into a nuclear magnetic resonance testing instrument for correction, then chromatographic bottle caps of calibration standards 1-5 are respectively removed and are placed into the support piece, the chromatographic bottle caps are in threaded connection with the bottle mouth of the chromatographic bottle, then the support piece is placed into the nuclear magnetic resonance testing instrument for testing a nuclear magnetic resonance signal, then the nuclear magnetic resonance signal and fluorine content are subjected to linear fitting to obtain a nuclear magnetic resonance signal-quality standard curve of the calibration standard sample, shown in figure 5, and the linear regression:
Y＝291596*X+9736.3
placing rubber with known fluorine element content of the fluororubber as a sample to be tested into a nuclear magnetic resonance instrument, testing a nuclear magnetic resonance signal, calculating the fluorine element content of the fluororubber according to the standard curve, and verifying the accuracy of the standard curve, wherein the known fluorine element content and the tested fluorine element content of the sample to be tested are shown in table 2;
TABLE 2 known and measured fluorine content of the samples to be tested
As can be seen from Table 2, the standard curve obtained by fitting the standard sample provided by the invention has high accuracy, and the obtained test sample has more accurate fluorine content.
Example 2
The embodiment provides a calibration standard sample for testing the content of fluorine element, a preparation method and an application thereof, and concretely comprises the following steps,
the calibration standard sample comprises a first calibration standard sample and a second calibration standard sample; the first calibration standard sample comprises tetrafluoroethanol, photosensitive adhesive, a chromatographic bottle, a first sealing element (polyetheretherketone) and a second sealing element (made of polyterephthalic acid);
the second calibration standard sample comprises fluorinated ethylene propylene, photosensitive glue, a chromatographic bottle, a first sealing element (polyether ether ketone) and a second sealing element (made of polyethylene terephthalate);
the preparation method of the calibration standard sample comprises the following steps,
the fluorinated ethylene propylene is processed into column bodies with the length of 30mm, the total number of the column bodies is 5, the column bodies are named as P ' 1, P ' 2, P ' 3, P ' 4 and P ' 5 from small to large according to the mass, and the mass of fluorine elements in the polymer is distributed in a gradient manner, see Table 3; then processing polyether-ether-ketone, wherein 6 polyether-ether-ketone are used as first sealing elements, and the first sealing elements are marked as B '1, B' 2, B '3, B' 4, B '5 and B' 6;
vacuumizing the photosensitive adhesive for 30min, injecting 3ml of tetrafluoroethanol into a 5ml chromatographic bottle by using an all-glass injector, dripping the photosensitive adhesive on the side wall of B' 1, and slightly screwing into the chromatographic bottle to enable the top end of the photosensitive adhesive to be 2mm lower than the top end of the chromatographic bottle; dripping photosensitive adhesive into the chromatographic bottle to the top end of the chromatographic bottle, illuminating for 20min to completely solidify the photosensitive adhesive, screwing a chromatographic bottle cap (a second sealing element), standing for 30h at room temperature to obtain a first calibration standard sample, and recording as a calibration standard sample 0';
respectively placing P '1, P' 2, P '3, P' 4 and P '5 into the chromatographic bottles, respectively dripping photosensitive glue on the side walls of the B' 2, B '3, B' 4, B '5 and B' 6, respectively screwing the chromatographic bottles to enable the top ends of the chromatographic bottles to be 2mm lower than the top ends of the chromatographic bottles, respectively dripping the photosensitive glue into the 5 chromatographic bottles to enable the photosensitive glue to be completely solidified by illumination for 20min, screwing down a chromatographic bottle cap (a second sealing element), and standing for 30h at room temperature to obtain second calibration standards which are respectively marked as calibration standards 1 '-5';
TABLE 3 quality of fluorinated ethylene propylene and its fluorine element
| Standard sample number | P’1 | P’2 | P’3 | P’4 | P’5 |
| Quality of standard sample material (g) | 1 | 1 | 1 | 1 | 1 |
| Mass (g) of fluorine element in standard sample | 0.224 | 0.378 | 0.514 | 0.635 | 0.719 |
The application of the first calibration standard sample and the second calibration standard sample, which are used for testing the fluorine element content of the fluororubber, specifically comprises the following steps:
after a chromatographic bottle cap of a calibration standard sample 0 ' is removed, the chromatographic bottle cap is placed in a support piece, the bottom of the support piece is provided with a threaded structure and is in threaded connection with the mouth of a chromatographic bottle, then the support piece is placed in a nuclear magnetic resonance testing instrument for correction, then chromatographic bottle caps of calibration standards samples 1 ' -5 ' are respectively removed and are placed in the support piece and are in threaded connection with the mouth of the chromatographic bottle, then the support piece is placed in the nuclear magnetic resonance testing instrument for testing nuclear magnetic resonance signals, then the nuclear magnetic resonance signals and fluorine content are subjected to linear fitting to obtain a nuclear magnetic resonance signal-quality standard curve of the calibration standard sample, and the linear regression equation of the standard curve is as follows, wherein the standard curve is as follows:
Y＝261536*X+7478.1
placing rubber with known fluorine element content of the fluororubber as a sample to be tested into a nuclear magnetic resonance instrument, testing a nuclear magnetic resonance signal, calculating the fluorine element content of the fluororubber according to the standard curve, and verifying the accuracy of the standard curve, wherein the known fluorine element content and the tested fluorine element content of the sample to be tested are shown in table 4;
TABLE 4 known and measured fluorine content of the samples to be tested
| Rubber sample to be tested | 1 | 2 | 3 | 4 | 5 |
| Sample Mass (g) | 0.852 | 0.837 | 0.905 | 0.799 | 0.932 |
| Nuclear magnetic resonance signal (dimensionless) | 137884.747 | 141123.183 | 154461.535 | 156030.753 | 178993.642 |
| Measurement of fluorine content (%) | 58.568 | 61.051 | 62.099 | 71.089 | 70.365 |
| The content of fluorine element (%) | 58 | 60 | 66 | 70 | 72 |
| Absolute deviation (%) | 0.568 | 1.051 | 3.901 | 1.089 | 1.6253 |
Comparative example 1
The comparative example provides a calibration standard sample of fluorine content and application thereof, and specifically comprises the following steps:
the calibration standard sample is fluororubber with known fluorine element content, the fluororubber is copolymerized by vinylidene chloride and perfluoropropylene, and the model is FPM 26;
the application of the calibration standard sample in the fluorine element content test of the fluororubber specifically comprises the following steps,
selecting FPM26 with the same mass and different fluorine content, and processing the FPM26 into block samples with the length of 3cm and the width of 1cm, wherein the block samples are numbered as 1, 2, 3, 4 and 5 in sequence; the No. 5 calibration standard sample is used as a calibration standard sample of the instrument, the No. 1-5 calibration standard sample is used for making a standard curve, and the fluorine element content of the calibration standard sample is shown in a table 5;
table 5 calibration standards and their quality of elemental fluorine
| Sample numbering | 1 | 2 | 3 | 4 | 5 |
| Sample Mass (g) | 1 | 1 | 1 | 1 | 1 |
| Mass (g) of fluorine element | 0.556 | 0.602 | 0.640 | 0.692 | 0.710 |
Putting a calibration standard sample into a nuclear magnetic resonance quartz test tube, putting the test tube into an instrument for testing to obtain a nuclear magnetic resonance signal, and then performing linear fitting on the nuclear magnetic resonance signal and the fluorine content to obtain a nuclear magnetic resonance signal-quality standard curve of the calibration standard sample, wherein the linear regression equation is shown in figure 7:
Y＝288899*X+11630
placing rubber with known fluorine element content of the fluororubber as a sample to be tested into a nuclear magnetic resonance instrument, testing a nuclear magnetic resonance signal, calculating the fluorine element content of the fluororubber according to the standard curve, and verifying the accuracy of the standard curve, wherein the known fluorine element content and the tested fluorine element content of the sample to be tested are shown in table 6;
TABLE 6 known and measured fluorine content of the samples to be tested
| Rubber sample to be tested | 1 | 2 | 3 | 4 | 5 |
| Sample Mass (g) | 0.852 | 0.837 | 0.905 | 0.799 | 0.932 |
| Nuclear magnetic resonance signal (dimensionless) | 137945.539 | 140791.547 | 150531.363 | 144323.568 | 190789.673 |
| Measurement of fluorine content (%) | 60.768 | 63.034 | 62.023 | 67.562 | 75.178 |
| The content of fluorine element (%) | 58 | 60 | 66 | 70 | 72 |
| Absolute deviation (%) | 2.768 | 3.034 | -3.977 | -2.438 | 3.178 |
Compared with the table 6, the liquid fluoropolymer is used as the first calibration standard sample, the solid fluoropolymer is used as the second calibration standard sample, the standard curve obtained by fitting is high in accuracy, and the detection result of the content of fluorine element is more accurate; in addition, the calibration standard sample provided by the invention can be repeatedly used for a long time.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A calibration standard sample for testing the content of fluorine elements is characterized by comprising a first calibration standard sample and a second calibration standard sample;
the first calibration standard comprises a liquid fluoropolymer; the second calibration standard includes a solid fluoropolymer.
2. The calibration standard of claim 1, wherein the liquid fluoropolymer is perfluorobenzene or tetrafluoroethanol.
3. Calibration standard according to claim 1 or 2, wherein the solid fluoropolymer is polytetrafluoroethylene, polyfluoroethylene propylene or polyvinylidene fluoride.
4. The calibration standard of any one of claims 1-3, wherein the first and second calibration standards further comprise first and second seals;
the first sealing element is made of a fluorine-free polymer, and the fluorine-free polymer is polymethyl methacrylate, polyether ether ketone or polystyrene; the second sealing element is made of fluorine-free plastic.
5. A method of sealing the calibration standard according to any one of claims 1 to 4, wherein the method of sealing the first calibration standard comprises adding a liquid fluoropolymer to a sample vial, sealing and allowing to stand to obtain the first calibration standard;
the sealing method of the second calibration standard sample comprises the steps of adding the solid fluoropolymer into a sample bottle, sealing and standing to obtain the second calibration standard sample.
6. The sealing method of claim 5, wherein the sealing method of the first calibration standard comprises adding liquid fluoropolymer into a sample bottle, dropping photosensitive glue on the outer side wall of a first sealing element, screwing into the open end of the sample bottle, dropping photosensitive glue on the top of the first sealing element, solidifying by illumination, covering a second sealing element, and standing to obtain the first calibration standard;
the sealing method of the second calibration standard sample comprises the steps of adding the solid fluoropolymer into a sample bottle, then dropwise adding the photosensitive adhesive on the outer side wall of the first sealing element, screwing the outer side wall into the open end of the sample bottle, dropwise adding the photosensitive adhesive on the top of the first sealing element, after light curing, covering the second sealing element, and standing to obtain the second calibration standard sample.
7. Use of a calibration standard according to any of claims 1 to 4 or a calibration standard obtained by a sealing method according to any of claims 5 to 6 for the detection of fluorine-containing samples.
8. Use according to claim 7, wherein the fluorine-containing sample is a fluoroelastomer.
9. Use according to claim 8, characterized in that it comprises, when testing the fluorine content of the fluororubber using a calibration standard, the first calibration standard being used for calibrating a nuclear magnetic resonance instrument; the second calibration standard is used for calibrating a standard curve of the fluorine element content.
10. Use according to claim 8 or 9, wherein the calibration standard is applied after it has been placed on the support and then tested;
the support is made of a fluorine-free polymer, and the fluorine-free polymer is polymethyl methacrylate, polyether ether ketone or polystyrene.
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