CN109946287B - Method for measuring platinum content in fluoropolymer - Google Patents
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- CN109946287B CN109946287B CN201810844919.7A CN201810844919A CN109946287B CN 109946287 B CN109946287 B CN 109946287B CN 201810844919 A CN201810844919 A CN 201810844919A CN 109946287 B CN109946287 B CN 109946287B
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Abstract
The invention provides a method for measuring the content of platinum in a fluoropolymer, which comprises the following steps: pretreating a solid sample to be detected by adopting fluorine gas/nitrogen gas mixed gas under the heating condition; carrying out sample dissolving treatment on the pretreated sample ash by using inorganic acid to obtain a solution sample to be detected; and detecting the platinum element of the solution sample to be detected by adopting an ICP-OES method to obtain the content of the platinum element in the sample. The method provided by the invention can fully digest the insoluble fluorine-containing polymer, thereby improving the detection accuracy, solving the defect that the platinum content is low when the existing digestion method is used for processing the fluorine-containing polymer, and being suitable for detecting the platinum content in polytetrafluoroethylene materials and fluorine-containing anti-fingerprint coatings.
Description
Technical Field
The invention belongs to the technical field of chemical analysis, and particularly relates to a method for measuring the content of platinum in a fluoropolymer.
Background
The fluorine-containing polymer is a high molecular material developed for military purpose in the 40 th of the 20 th century, and with the progress of science and technology, the fluorine-containing polymer is greatly developed, and the application field of the fluorine-containing polymer is rapidly expanded. Fluoropolymer research was first initiated by Dupont in the united states, who first developed Polytetrafluoroethylene (PTFE) (r.j. plunkett, us Pat.2230654, 1939.), pulling on the research initiative for fluoropolymers, and by 1946 the polytetrafluoroethylene products began to show up in the market. In the sixties, the fluorine coating taking polytetrafluoroethylene as the matrix is applied to cooking products, and the prepared cookers such as non-stick pans and the like have good market effect. The subsequent coating based on polyvinylidene fluoride (PVDF) has gained importance in the architectural and decorative coatings industry due to its superior weatherability. In the seventies, the room temperature curing vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene thermoelastic terpolymer appeared, and in 1982, the Ashi Glass company also introduced the second generation product of PVDF, namely a solvent-based coating taking an alternating copolymer of fluoroolefin and alkyl vinyl ether as a matrix, so that the fluoropolymer product is diversified, the application field is wide, and a relatively complete product series is formed in the following decades.
The fluorine-containing polymer has excellent weather resistance, durability and chemical resistance, and also has excellent properties of high surface activity, hydrophobicity and oleophobicity, pollution resistance, non-stickiness and the like. Therefore, fluoropolymers are widely used in various aspects of human society.
In the preparation process of the fluorine-containing polymer (fluorine-containing high molecular compound) and the production process of raw materials, platinum (Pt) is frequently used as a raw material or a catalyst, so that platinum in the fluorine-containing polymer is remained, and if the content of the remained platinum reaches a certain value, harmful catalytic reactions are initiated, so that the property of the fluorine-containing polymer is changed, and the service performance of the fluorine-containing polymer is influenced. Such as: fluorine-containing anti-fingerprint coating materials are reported in patents CN106810684A and CN106866972A, and the key step is the hydrosilylation reaction of fluorine-containing olefin and siloxane (such as trimethyl siloxane), and a platinum-containing compound is used as a catalyst (Karstedt's catalyst) in the synthesis process to successfully realize the reaction, as shown below.
During the preparation of fluorine-containing polymer, platinum element in the catalyst can be entrained and occluded in the product, and the performance of the product is influenced. It is necessary to analyze the content of platinum in the product and then to try to remove the platinum element in the product. Some fluoropolymers are functional materials in which platinum accumulates during use, resulting in an increase in the platinum content of the fluoropolymer. Such as: the membrane of the methanol fuel cell is a fluorine-containing high polymer film (perfluorinated ion sulfonic acid film), and platinum on an electrode can be deposited in the membrane of the cell in the use process of the cell, so that the performance of the cell is changed, and even safety accidents are caused. It is therefore important to eliminate the presence of platinum in fuel cell membranes, where it is first necessary to measure the amount of platinum, know it, and then try to overcome the problem of platinum deposition.
The existing methods for detecting the platinum content comprise a chemical analysis method and an instrumental analysis method, the instrumental analysis method is more convenient and reliable to use than the chemical analysis method, and the instrumental analysis method mainly refers to a spectral analysis method: including infrared spectroscopy, ultraviolet spectroscopy, atomic spectroscopy, and X-ray fluorescence spectroscopy. Atomic spectroscopy is a widely adopted method for analyzing platinum element at present, and is divided into atomic Emission spectroscopy and atomic absorption spectroscopy, and with the successful application of an Inductively Coupled Plasma (ICP) light source in Emission spectroscopy, Inductively Coupled Plasma Emission spectroscopy (ICP-OES) has become one of the most important elemental analysis means instead of atomic absorption spectroscopy. The ICP-OES emission spectrum analysis technology has the following characteristics (advantages):
(1) the multi-element analysis can be rapidly carried out simultaneously, and up to 73 elements in the periodic table can be measured;
(2) the detection sensitivity is high, including elements which are easy to form refractory oxides, and the detection limit can reach per milliliter and submicron;
(3) the matrix effect is low, the analysis method is easy to establish, the standard curve has a wide linear dynamic range, and the method has good precision and repeatability.
Therefore, the qualitative and quantitative analysis of platinum mainly adopts inductively coupled plasma emission spectrometer (ICP-OES) analysis. The qualitative analysis of platinum can be directly carried out by using a solid sample, but for the quantitative analysis of platinum element, the solid sample containing platinum element must be dissolved into a solution before the quantitative analysis of platinum element can be carried out.
in the atomic spectrometry analysis, the dissolution of the sample refers to the decomposition of the sample, which refers to the preparation of a solution suitable for the next operation (measurement and pretreatment before measurement) by subjecting an object (sample) to chemical analysis and test to appropriate chemical treatment.
The common digestion methods for the solid sample in ICP-OES atomic emission spectrometry comprise three methods, namely dissolution, digestion under a violent condition and dry ashing, and are as follows:
(1) adopting a solution (solvent) dissolving method:
dissolution refers to a sample processing method in which various liquid chemical reagents including water and a sample (usually a solid) are used to decompose the sample by means of chemical reaction under a certain temperature and pressure, so that components to be tested are converted into ionic forms and exist in a digestion solution for testing. It is the most widely used, simple and convenient sample processing method with the longest history. The dissolution operation is simple and convenient, and the sample is added into a proper liquid reagent and stirred (sometimes heated). The liquid reagent is mainly an acid, and other solvents such as bases, complexes, oxidizing or reducing agents and organic solvents are sometimes used.
In the presence of acid or alkali, some oxidant (such as potassium permanganate, hydrogen peroxide) or catalyst (such as copper sulfate, mercury sulfate, selenium dioxide, and vanadium pentoxide) is added as necessary, and the common acid is concentrated hydrochloric acid, concentrated nitric acid, concentrated sulfuric acid, perchloric acid, aqua regia, etc. In the actual wet digestion, either only one kind of acid or a mixed acid may be used. The solid sample containing platinum is dissolved in aqua regia to prepare a solution.
(2) Digestion method under violent condition (high temperature, high pressure digestion, microwave digestion)
High-temperature and high-pressure digestion: the method is based on the normal pressure wet digestion method, and comprises the steps of sealing and pressurizing, putting a sample and acid in a closed special pressure digestion container, and decomposing the sample under a certain pressure and a proper temperature. It is a sealed digestion method developed for overcoming the volatile loss and easy pollution of a digesting agent and volatile elements in a normal pressure wet digestion method.
First Knapp began to use High-Pressure gelation (HPA technology), which is not only time-saving, but also opens new avenues for particularly intractable samples. The HPA technique is carried out in quartz vessels at temperatures up to 320 ℃ and pressures up to 100bar (1.0bar 105Pa), even thermally stable organics can be digested with acid at these temperatures, and most samples can be completely digested by this method.
Since the oxidation capacity of the digestion reagent is strongly dependent on temperature, a distinction can be made between "simple" pressure digestion, where temperatures do not exceed 180 ℃ and high-pressure digestion, where pressures greater than 70bar may exceed 300 ℃.
In CN101626643A (a microwave-assisted heating body machine manufacturing method, 2010) in chenjie, liuzhi, the invention discloses that a microwave-assisted heating body is arranged in a reactor and immersed in a reaction solution, so that the reaction speed of a sample can be improved, the reaction time can be shortened, and the method is particularly suitable for digestion treatment of organic matters with poor microwave absorption of the sample and samples obtained by organic synthesis.
The invention of the patent CN103418324B (a microwave digestion device, 2013.) discloses a microwave digestion device, which adopts a pressure-resistant tank and a polytetrafluoroethylene material which can be penetrated by microwaves as a lining material, can process samples under high pressure, and solves the safety problem of microwave digestion under high pressure.
However, even under such severe conditions, it is difficult to digest the fluoropolymer, and even if a solution is obtained, a fluorine-containing compound remains in the prepared sample solution, which affects the analysis of platinum element at the later stage, and further, the fluoropolymer cannot be completely digested, resulting in occlusion of platinum element in solid residue, which affects the accuracy of the analysis.
(3) Dry ashing:
the essence of dry ashing (pyrolysis, muffle ashing) is the oxidative decomposition of the sample at high temperatures, a classical method commonly used to remove organic matrix from the sample for further determination of metals in organic materials.
The ashing temperature is generally 500-600 ℃, and impurities introduced into the crucible can cause sample pollution due to the temperature rise. The sample size, dry sample, is generally no more than 10 grams, fresh sample is no more than 50 grams. Too large a sample amount easily causes ashing difficulty or too long a time, which introduces new errors. Conversely, too little may also introduce errors in sample non-uniformity. The time is usually controlled to be 4 to 8 hours. The sample containing much fat and sugar takes a long time, while the sample containing much cellulose and protein takes a short time. Whether ashing is complete is generally judged by the color of the ash. Ashing is considered complete when the ash is white or off-white in color but does not contain carbon particles.
The method is suitable for measuring samples with high organic content such as food, plant samples and the like, and is not suitable for measuring soil and mineral samples. Most of the metal element content analysis is suitable for dry ashing, but mercury, lead, cadmium, tin, selenium and the like are easily volatilized and lost under the high-temperature condition, so that the method is not suitable for use.
The three common sample digestion methods are difficult to treat the fluorine polymer containing platinum, difficult to completely dissolve the fluorine polymer and have the defect of low content measurement of platinum element.
In addition, the solid sample of fluoropolymer is not well treated, organic fluorine-containing compounds remain in the sample, and the ICP-OES emission spectrum analysis has the following disadvantages and problems:
after the organic fluorine-containing compound enters the ICP, free carbon generated by decomposition at high temperature is easy to form carbon particles to deposit on a pipe orifice, and the stable operation and the spectral measurement of plasma are influenced.
Organic fluorine-containing compounds, when introduced into the ICP, give rise to many molecular bands in the spectrum and produce a very deep spectral background in some bands.
The introduction of the organic fluorine-containing compound into the ICP light source significantly changes the reflected impedance of the plasma, thereby changing the impedance matching state of the plasma load and the high frequency generator. In severe cases, the plasma can be unstable and even completely extinguished, and the rectangular tube of the ICP-OES instrument can be corroded and burnt down in some cases.
Disclosure of Invention
The invention aims to provide a method for measuring the content of platinum in a fluoropolymer, and aims to solve the problems that the existing method for measuring the content of platinum in a solid sample in ICP-OES atomic emission spectrometry is low in platinum content measurement and cannot be used for a hardly-soluble platinum-containing fluoropolymer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for measuring the content of platinum in a fluoropolymer, which comprises the following three steps:
s01) adopting fluorine gas/nitrogen gas mixed gas to pre-process the solid sample to be detected under the heating condition;
s02) carrying out sample dissolving treatment on the ash content of the pretreated sample by using inorganic acid to obtain a solution sample to be detected;
s03) detecting the platinum element of the solution sample to be detected by adopting an ICP-OES method, and obtaining the content of the platinum element in the sample.
According to the method for measuring the platinum content in the fluoropolymer, provided by the invention, a solid sample to be measured is pretreated under the condition of fluorine gas/nitrogen mixed gas, so that the fluoropolymer is changed into carbon tetrafluoride, hydrogen fluoride and the like at high temperature; further digesting under the action of inorganic acid to prepare a platinum-containing solution sample to be detected. And further detecting the solution sample to be detected containing platinum by adopting an ICP-OES method to obtain the content of the platinum element in the insoluble fluorine-containing polymer sample. The method provided by the invention can fully digest the insoluble fluorine-containing polymer, thereby improving the detection accuracy, solving the defect that the platinum content is low when the fluorine-containing polymer is processed by the existing digestion method, and being suitable for detecting the platinum content in polytetrafluoroethylene materials and fluorine-containing anti-fingerprint coatings. In addition, the method provided by the invention can conveniently and quickly digest the fluorine-containing polymer and can be used for measuring other elements which are difficult to volatilize in the fluorine-containing polymer.
Drawings
FIG. 1 is a schematic structural diagram of a fluorine gas high-temperature dynamic digestion device provided by an embodiment of the invention;
FIG. 2 is a graph showing a standard curve of a platinum solution provided in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a method for measuring the content of platinum in a fluorine polymer, which comprises the following three steps:
s01), adopting fluorine gas/nitrogen gas mixed gas to pre-treat the solid sample to be detected under the heating condition;
s02), carrying out sample dissolving treatment on the ash content of the pretreated sample by using inorganic acid to obtain a solution sample to be detected;
s03), detecting the platinum element of the solution sample to be detected by adopting an ICP-OES method, and obtaining the content of the platinum element in the sample.
According to the method for determining the platinum content in the fluoropolymer provided by the embodiment of the invention, a solid sample to be detected is pretreated under the condition of fluorine gas/nitrogen mixed gas, so that the fluoropolymer is changed into carbon tetrafluoride, hydrogen fluoride and the like at high temperature; further digesting under the action of inorganic acid to prepare a platinum-containing solution sample to be detected. And further detecting the solution sample to be detected containing platinum by adopting an ICP-OES method to obtain the content of the platinum element in the insoluble fluorine-containing polymer sample. The method provided by the embodiment of the invention can fully digest the insoluble fluorine-containing polymer, thereby improving the detection accuracy, solving the defect that the platinum content is low when the fluorine-containing polymer is processed by the existing digestion method, and being suitable for detecting the platinum content in polytetrafluoroethylene materials and fluorine-containing anti-fingerprint coatings. In addition, the method provided by the embodiment of the invention can conveniently and quickly digest the fluorine-containing polymer and can be used for measuring other elements which are difficult to volatilize in the fluorine-containing polymer.
Specifically, in step S01, the fluorine gas/nitrogen gas mixed gas is introduced into the digestion apparatus. Preferably, the fluorine gas/nitrogen gas mixed gas has a volume percentage of 1.0% to 30% based on 100% of the total volume of the fluorine gas/nitrogen gas mixed gas. The fluorine gas in the embodiment of the invention mainly has the function of burning and decomposing the fluorine-containing polymer into carbon tetrafluoride gas. If the content of the fluorine gas is too low, the fluorine-containing polymer is incompletely combusted, and the accuracy of the detection result of the solid sample to be detected is influenced; if the fluorine gas content is too high, explosive combustion may occur, which is dangerous. More preferably, the fluorine gas accounts for 10 to 30 percent of the total volume of the fluorine gas/nitrogen gas mixed gas.
Further preferably, in the embodiment of the present invention, the fluorine/nitrogen mixed gas is introduced into the heating device at a certain flow rate, and the flow rate of the fluorine/nitrogen mixed gas may be 1.0 to 1000ml/min, and is preferably 10 to 100ml/min, so as to ensure that the solid sample to be tested is smoothly combusted in the fluorine flow, and further ensure the stability and accuracy of the test result.
In the embodiment of the invention, the solid sample to be detected is put into a heating zone of the digestion device, preferably in a batch adding manner, so that the solid sample to be detected is pretreated and digested under uniform and stable conditions. Preferably, the single release amount of the solid sample to be detected is 1.0-200g, and more preferably 50-100 g.
The pretreatment conditions of the solid sample to be detected under the heating condition are as follows: heating to 800-3000 ℃, and pretreating the solid sample to be detected. Under the action of fluorine gas and high temperature, the fluorine-containing polymer is rapidly combusted to become carbon tetrafluoride, hydrogen fluoride and other gases. More preferably, the solid sample to be detected is pretreated at 2000-3000 ℃, so that the fluorine-containing polymer is efficiently and fully combusted. After the sintering, the platinum element of the solid sample to be tested exists in the ash after the combustion.
In step S02, after the sample is burned and sintered, the ash content after the combustion of the inorganic acid is used for sample dissolution treatment, and the burned sample is dissolved and collected. Preferably, the inorganic acid is at least one selected from concentrated hydrochloric acid, concentrated nitric acid, concentrated sulfuric acid, perchloric acid and aqua regia, and is more preferably aqua regia. Further preferably, the amount of the inorganic acid is such that the mass-to-volume ratio (g/ml) of the solid sample to be tested to the inorganic acid is 1: 1-50 (the amount of the inorganic acid is far larger than that of the sample) so as to fully dissolve and collect products and gray matter of the burnt solid sample to be detected, avoid the loss of the digestion components of the fluorine-containing polymer, simultaneously ensure the moderate concentration of the obtained solution sample to be detected and improve the accuracy of the measurement of the platinum element content of the sample to be detected. More preferably, the mass-to-volume ratio (g/ml) of the solid sample to be tested to the inorganic acid is 1: 5-20.
In the step S03, the ICP-OES method is used to detect the platinum element in the solution sample to be tested, and may be performed by using a commercially available ICP-OES testing apparatus. As a specific example, an ICP-OES testing instrument adopts a German SPECTRA ARCOS full spectrum direct reading plasma emission spectrometer; the ICP-OES test conditions are as follows:
the instrument parameters are as follows: the observation height is 2 mm; the flow rate of the atomizer is 0.75L/min; power: 1430W; plasma gas 12L/min; the auxiliary gas flow is 0.9L/min; reference wavelength, platinum 214.423 nm.
In the embodiment of the invention, the platinum content in the fluoropolymer is measured by a fluorine gas high-temperature dynamic digestion device. Preferably, as shown in fig. 1, the high temperature dynamic digestion device comprises a combustion system 1 and an ash collection system 3 which are communicated through a calcium fluoride glass tube 2, wherein the combustion system 1 comprises an induction furnace 11 for placing the solid sample to be measured to be heated and digested, the induction furnace 11 forms a high frequency induction heating zone 12 (the high frequency induction heating zone is a space zone heated by an electromagnetic induction coil) for heating and digesting the solid sample to be measured at the central position, wherein the induction furnace 11 is a sealable induction furnace and provides a space for the solid sample to be measured to burn in a fluorine/nitrogen mixed gas atmosphere. In addition, the induction furnace 11 is made of calcium fluoride, so that the induction furnace can resist the high temperature of 3000 ℃ in the embodiment of the invention without decomposition, and the detection accuracy is ensured. The high-frequency induction heating area 12 is heated by a high-frequency induction coil, so that the temperature of flame reaches 800-3000 ℃, enough heat energy is provided for digestion of the solid sample to be detected, and the high-frequency induction heating area 12 is preferably arranged at the center of the induction furnace 11. Further preferably, the calcium fluoride material induction furnace 11 is in a shuttle shape, the high-frequency induction heating area 12 is also in a shuttle structure, and the vertical distance between each point on the wall surface of the high-frequency induction heating area 12 and the inner wall of the calcium fluoride material induction furnace 11 is the same, so that the heating uniformity and the digestion uniformity of the solid sample to be detected can be ensured, and the stability of the reaction system can be better controlled.
In the embodiment of the present invention, the induction furnace 11 is provided with an inlet 111 for sample injection and introduction of fluorine/nitrogen mixed gas, and an outlet 112 for communicating with one end of the calcium fluoride glass tube 2. When the induction furnace 11 is in a shuttle shape, the inlet 111 and the outlet 112 are respectively located at two ends of the shuttle body which are farthest away.
In the embodiment of the present invention, the induction furnace 11 has a double-tube torch 13 in contact with the high-frequency induction heating zone 12, the high-frequency induction heating zone 12 is disposed in a space region above the double-tube torch 13, and a nitrogen gas flow channel is formed between two tubes of the double-tube torch 13. The double-barrel flare torch tube 13 is made of calcium fluoride, so that the double-barrel flare torch tube 13 can resist the high temperature of 3000 ℃ of the embodiment of the invention without decomposition, and the detection accuracy is ensured. Nitrogen is introduced between the two barrels of the double-barrel torch pipe 13, and the nitrogen is introduced between the two barrels to reduce the temperature at the periphery of the induction area, so that the temperature around the combustion flame of the solid sample (fluoropolymer) to be detected is reduced, and the phenomenon that the induction furnace 11 is damaged due to the fact that calcium fluoride serving as a lining material of the induction furnace 11 is melted due to overhigh temperature is avoided.
In the embodiment of the invention, a cooling layer 14 is arranged outside the induction furnace 11, the cooling layer is a sealable cavity structure formed by enclosing the outer wall of the induction furnace 11, and a cooling water inlet and a cooling water outlet are respectively arranged at two ends of the cooling layer close to the inlet and the outlet. The temperature of the outer wall of the induction furnace 11 is cooled by injecting cooling water flowing through the cooling layer 14.
In the embodiment of the invention, a combustion system 1 and an ash collection system 3 are communicated through a calcium fluoride glass tube 2. The calcium fluoride glass tube 2 guides the product generated from the induction furnace 11 (combustion chamber) to a collection system for collection, and at the same time, cools the product.
In the embodiment of the present invention, the ash collection system 3 includes a two-way receiving bottle 31, the two-way receiving bottle 31 is made of calcium fluoride, and one opening of the two-way receiving bottle 31 is communicated with the other end of the calcium fluoride glass tube 2 and is used for receiving a high-temperature digested product introduced from the calcium fluoride glass tube 2. The other opening of the two-way receiver flask 31 communicates with one end of a condenser tube 32, and the condenser tube 32 can further cool the product entering the two-way receiver flask 31. The other end of the condensation pipe 32 is communicated with a tail gas collecting device 33.
The following description will be given with reference to specific examples.
Reagent:
1000mg/L platinum standard substance; nitric acid (analytically pure); hydrochloric acid (analytically pure), deionized water and aqua regia.
Example 1
Preparation of a standard solution:
the standard solution of platinum (1000 mg/L) was diluted to 0.1mg/L,0.2mg/L,0.5mg/L,1.0mg/L and plotted as a standard curve for platinum content, as shown in FIG. 2. The linear coefficient of the standard curve is 0.99986, and the detection limit is 0.0025mg/L (solution concentration).
Example 2
A method for measuring the content of platinum in a fluoropolymer is a high-temperature dynamic digestion method for fluorine gas, and comprises the following steps:
s21, introducing 30% fluorine-nitrogen mixed gas into a digestion device at a flow rate of 20ml/min, and then heating the temperature of a heating zone to about 2500 ℃; 51.531 g of sample is added in batches through a sample inlet, and through the rapid combustion of high-temperature fluorine gas in a combustion chamber, the fluorine-containing polymer is changed into carbon tetrafluoride, hydrogen fluoride and other gases at high temperature to be burnt;
s22, after the sample is combusted and sintered, dissolving and cleaning the sample, a combustion chamber, a glass tube, a collecting bottle and a condenser tube 32 by adopting 100ml of aqua regia to prepare a to-be-detected solution sample containing platinum solution;
s23, detecting the platinum element of the solution sample to be detected by adopting an ICP-OES method to obtain the content of the platinum element in the sample. An ICP-OES test instrument adopts a German SPECTRA ARCCOS full spectrum direct reading plasma emission spectrometer; the ICP-OES test conditions are as follows: the instrument parameters are as follows: the observation height is 2 mm; the flow rate of the atomizer is 0.75L/min; power: 1430W; plasma gas 12L/min; the auxiliary gas flow is 0.9L/min; reference wavelength, platinum 214.423 nm.
Comparative example 1
Nitric acid wet-process nitrolysis: about 5.031g of sample is weighed into a beaker, 50mL of nitric acid is added, the petri dish is covered, and the beaker is preheated for 30min at 100 ℃. Heating to 150 deg.C, and keeping the temperature for 30 min. The watch glass is removed, the nitric acid is evaporated to leave about 2mL, and the volume is adjusted to 50mL after cooling.
Comparative example 2
Aqua regia wet-method nitrolysis: about 5.031g of sample is weighed into a beaker, 50mL of aqua regia is added, the cuvette is covered, and pre-heated at 100 ℃ for 30 min. Heating to 150 deg.C, and keeping the temperature for 30 min. The watch glass was removed, the solution was evaporated to leave about 2mL, and the volume was adjusted to 50mL after cooling.
Comparative example 3
Microwave heating aqua regia nitrolysis: about 5.031g of sample is weighed into a beaker, 50mL of aqua regia is added, the cuvette is covered, and pre-heated at 100 ℃ for 30 min. The microwave is continuously added for 30 min. The watch glass was removed, the solution was evaporated to leave about 2mL, and the volume was adjusted to 50mL after cooling.
Comparative example 4
Dry ashing: about 15.085g of a sample was weighed into a quartz crucible, 50mL of nitric acid was added, the sample was carbonized by heating to 200 ℃ for 30min on an electric furnace, about 2mL of nitric acid remained after evaporation, and the sample was ashed in a muffle furnace at 600 ℃ for 6 hours. And taking out the sample after cooling, adding 2mL of aqua regia to dissolve ash, and fixing the volume to 50 mL.
The results of three tests on the platinum content in perfluoropolyether compounds measured in example 2 and comparative examples 1 to 4 of the present invention were averaged, and the analysis results are shown in table 1 below.
TABLE 1
As can be seen from table 1 above, compared with a wet method for processing a sample (the sample cannot be oxidized by nitric acid or aqua regia to form an inorganic ion solution, a large amount of the sample remains in a colloidal state in the solution, trace platinum elements may still be included by the sample and cannot migrate into the solution, the measurement result has large fluctuation and is lower than an actual value), and a dry ashing method for processing the sample (perfluoropolyether substances cannot be completely carbonized, the sample is directly decomposed at a high temperature, and almost no ash exists in a crucible, the trace platinum elements may be taken away along with the decomposed sample, and the measurement result has large fluctuation and is lower than the actual value).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A method for measuring the content of platinum in a fluoropolymer comprises the following steps:
pretreating a solid sample to be detected by adopting fluorine gas/nitrogen gas mixed gas under the heating condition;
carrying out sample dissolving treatment on the pretreated sample ash by using inorganic acid to obtain a solution sample to be detected;
detecting the platinum element of the solution sample to be detected by adopting an ICP-OES method to obtain the content of the platinum element in the sample;
wherein, in the fluorine gas/nitrogen gas mixture, the volume percentage of the fluorine gas is 1.0-30% calculated by taking the total volume of the fluorine gas/nitrogen gas mixture as 100%;
the pretreatment conditions of the solid sample to be detected under the heating condition are as follows: heating to 800-3000 ℃, and pretreating the solid sample to be detected.
2. The method according to claim 1, wherein the inorganic acid is at least one selected from the group consisting of concentrated hydrochloric acid, concentrated nitric acid, concentrated sulfuric acid, perchloric acid, and aqua regia.
3. The method for measuring the platinum content in the fluoropolymer according to any one of claims 1 to 2, wherein the platinum content in the fluoropolymer is measured by a fluorine gas high temperature dynamic digestion apparatus.
4. The method for determining the platinum content in the fluoropolymer according to claim 3, wherein the high-temperature dynamic digestion device comprises a combustion system and an ash collection system which are communicated through a calcium fluoride glass tube, wherein the combustion system comprises an induction furnace for placing the solid sample to be heated and digested, and the induction furnace is centrally provided with a high-frequency induction heating zone for heating and digesting the solid sample to be heated and digested, wherein the induction furnace is a sealable calcium fluoride induction furnace, and the high-frequency induction heating zone is arranged at the center of the induction furnace.
5. The method of claim 4, wherein the induction furnace is provided with an inlet for sample introduction and introduction of the fluorine/nitrogen gas mixture and an outlet for communication with one end of the calcium fluoride glass tube.
6. The method of claim 5, wherein the induction furnace has a twin torch tube in contact with the high-frequency induction heating zone, and a nitrogen gas flow channel is formed between the two tubes of the twin torch tube.
7. The method according to claim 5, wherein a cooling layer is provided outside the induction furnace, the cooling layer has a cavity structure formed around the outer wall of the induction furnace, and the cooling layer has a cooling water inlet and a cooling water outlet at both ends adjacent to the inlet and the outlet, respectively.
8. The method for determining the content of platinum in the fluoropolymer according to claim 4, wherein the ash collection system comprises a two-way receiving bottle, one opening of the two-way receiving bottle is communicated with the other end of the calcium fluoride glass tube, the other opening of the two-way receiving bottle is communicated with one end of a condensation tube, and the other end of the condensation tube is communicated with a tail gas collection device.
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