CN117949523A - Method for detecting metal elements in carbon fiber impurities - Google Patents
Method for detecting metal elements in carbon fiber impurities Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 130
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 96
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000012535 impurity Substances 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 93
- 239000000243 solution Substances 0.000 claims abstract description 82
- 238000001514 detection method Methods 0.000 claims abstract description 64
- 239000012086 standard solution Substances 0.000 claims abstract description 46
- 238000012360 testing method Methods 0.000 claims abstract description 32
- 239000012490 blank solution Substances 0.000 claims abstract description 31
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000184 acid digestion Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 230000010354 integration Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000000523 sample Substances 0.000 description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- 229910052697 platinum Inorganic materials 0.000 description 14
- 238000011084 recovery Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000012795 verification Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 titanium metals Chemical class 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a method for detecting metal elements in carbon fiber impurities, which comprises the following steps: pretreating a carbon fiber sample, and preparing the carbon fiber sample into a solution to obtain a solution to be detected of the carbon fiber sample; detecting the solution to be detected under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a detection result of the solution to be detected; calculating the content of each metal element in the carbon fiber sample according to a standard curve equation of each metal element, a detection result of a blank solution and a detection result of a solution to be detected; the standard curve equation of each metal element is obtained by fitting a first detection result of a standard solution containing each metal element at a plurality of different concentrations and the concentration of the metal element in each standard solution. The scheme not only can realize the detection of various metal element types, but also has the advantages of simple method, lower detection limit, better sensitivity, higher accuracy, better repeatability and wide application range.
Description
Technical Field
The invention relates to the technical field of metal element content, in particular to a method for detecting metal elements in carbon fiber impurities.
Background
The impurities in the carbon fiber mainly come from the precursor and the production process thereof, and a large amount of elements such as silicon, a small amount of other alkali metals and the like exist in the sizing agent used in the production process. The content of impurity elements such as silicon, potassium, sodium, calcium, magnesium, iron, aluminum, titanium and the like in the carbon fiber has larger influence on the oxidation resistance, and the higher the content of alkali metal and alkaline earth metal in the carbon fiber is, the worse the oxidation resistance is, the higher the oxidation weight loss rate is, so that the quality of the carbon fiber is influenced; therefore, the oxidation resistance of the carbon fiber can be measured by detecting the impurity metal elements in the carbon fiber.
In the related art, an atomic absorption spectrometry is generally used for detecting metal elements in carbon fiber impurities, however, the method cannot be applied to carbon fiber impurity detection with low impurity metal element content and a large impurity metal element variety.
Accordingly, in view of the above-mentioned problems, there is a need to provide a novel method for detecting metal elements in carbon fiber impurities.
Disclosure of Invention
The embodiment of the invention provides a method for detecting metal elements in carbon fiber impurities, which can solve the problems of lower sensitivity and fewer detected metal element types of the method for detecting the metal element content in the related technology.
In a first aspect, an embodiment of the present invention provides a method for detecting a metal element in a carbon fiber impurity, including:
pretreating a carbon fiber sample, and preparing the carbon fiber sample into a solution to obtain a solution to be detected of the carbon fiber sample;
Detecting the solution to be detected under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a detection result of the solution to be detected;
Calculating the content of each metal element in the carbon fiber sample according to a standard curve equation of each metal element, a detection result of a blank solution and a detection result of the solution to be detected; the standard curve equation of each metal element is obtained by fitting a first detection result of a standard solution containing each metal element at a plurality of different concentrations and the concentration of the metal element in each standard solution.
Preferably, the preparation method of the solution to be detected comprises the following steps:
(1) Cutting the carbon fiber sample to obtain carbon fiber fragments;
(2) Calcining and acid digestion are sequentially carried out on the carbon fiber fragments to obtain a sample to be detected;
(3) Adding nitric acid into the sample to be detected, heating for dissolving and fixing the volume to obtain the solution to be detected.
Preferably, in step (1), the carbon fiber fragments have a particle size of less than 2cm.
Preferably, in the step (2), the calcination is performed at a temperature of 700 to 750 ℃ for a time of 10 to 12 hours.
Preferably, in step (2), the acid digestion uses an acid solution of perchloric acid and hydrofluoric acid; wherein, the volume ratio of perchloric acid to hydrofluoric acid is 1: (3-4).
Preferably, in the step (2), the temperature of the acid digestion is 235-245 ℃ and the time is 1.5-2 h.
Preferably, in the step (3), the temperature of the heating dissolution is 70-80 ℃ and the time is 5-10 min.
Preferably, the standard curve equation of each metal element is obtained by fitting in the following manner:
Preparing a blank solution and a plurality of standard solutions with different concentrations respectively; wherein the standard solution is a solution respectively containing one metal element, and the blank solution is a solution without the metal element; the metal elements are potassium, sodium, calcium, magnesium, iron, aluminum and titanium;
detecting the standard solution and the blank solution under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a second detection result corresponding to the blank solution and a first detection result corresponding to each standard solution;
And fitting to obtain a standard curve equation of each metal element according to each first detection result and the concentration of the metal element in each standard solution.
Preferably, the preset test conditions include:
adopting a Helium KED analysis mode;
The radio frequency power is 1600W, the integration time is 1000ms, the temperature of an atomization chamber is 2 ℃, the flow rate of plasma gas is 15L/min, the flow rate of carrier gas is 1.04mL/min, the flow rate of He gas is 4-5 mL/min, the rotating speed of a peristaltic pump is 35rpm, the lifting rate of a sample is 0.3r/s, and the repetition times are 2-3 times.
Preferably, the calculating the content of each metal element in the carbon fiber sample according to the standard curve equation of each metal element, the detection result of the blank solution and the detection result of the solution to be detected includes:
Obtaining the concentration of each metal element in the carbon fiber sample based on the standard curve equation of each metal element and the detection result of the solution to be detected;
And calculating the content of each metal element in the carbon fiber sample according to the concentration of each metal element and the detection result of the blank solution.
Preferably, the content of each metal element in the carbon fiber sample is calculated by the following formula:
Wherein w is the mass fraction of the metal element to be detected in the carbon fiber sample, and the unit is; c is the mass concentration of the detected metal element in the solution to be detected and the mass concentration of the detected metal element in the blank solution, wherein the unit is mug/mL; m is the mass of the carbon fiber fragments, and the unit is g; v is the total volume of the solution to be detected, and the unit is mL; v 1 is the partitioned volume of the solution to be detected, and the unit is mL; v 2 is the test liquid volume of the solution to be tested, in mL.
Compared with the prior art, the invention has at least the following beneficial effects:
Firstly, preprocessing a carbon fiber sample, preparing the carbon fiber sample into a solution to be detected, detecting metal elements in the solution to be detected under specific test conditions by using an inductively coupled plasma mass spectrometer, and finally calculating the content of each metal element in the carbon fiber sample according to a standard curve equation of each metal element, a detection result of a blank sample and a detection result of the solution to be detected, which are obtained by fitting; according to the invention, a reasonable pretreatment method is adopted to treat the carbon fiber sample, and the inductively coupled plasma mass spectrometry is combined so as to realize the detection of the contents of various metal elements in the sample to be detected.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for detecting metal elements in carbon fiber impurities according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
In order to solve the problems of low sensitivity and few types of metal elements in the detection method of metal element content in the related art, as shown in fig. 1, an embodiment of the present invention provides a detection method of metal element in carbon fiber impurities, which includes:
step 100, preparing a carbon fiber sample into a solution after pretreatment, and obtaining a solution to be detected of the carbon fiber sample;
102, detecting the solution to be detected under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a detection result of the solution to be detected;
104, calculating the content of each metal element in the carbon fiber sample according to a standard curve equation of each metal element, a detection result of a blank solution and a detection result of the solution to be detected; the standard curve equation of each metal element is obtained by fitting a first detection result of a standard solution containing each metal element at a plurality of different concentrations and the concentration of the metal element in each standard solution.
In the embodiment of the invention, firstly, a carbon fiber sample is preprocessed and then prepared into a solution to be detected, then, metal elements in the solution to be detected are detected under specific test conditions by utilizing an inductively coupled plasma mass spectrometer (ICP-MS), and finally, the content of each metal element in the carbon fiber sample can be calculated according to a standard curve equation of each metal element, a detection result of a blank sample and a detection result of the solution to be detected, which are obtained by fitting; according to the invention, a reasonable pretreatment method is adopted to treat the carbon fiber sample, and the inductively coupled plasma mass spectrometry is combined so as to realize the detection of the contents of various metal elements in the sample to be detected.
According to some preferred embodiments, the preparation method of the solution to be detected comprises:
(1) Cutting the carbon fiber sample to obtain carbon fiber fragments;
(2) Calcining and acid digestion are sequentially carried out on the carbon fiber fragments to obtain a sample to be detected;
(3) Adding nitric acid into the sample to be detected, heating for dissolving and fixing the volume to obtain the solution to be detected.
In this embodiment, before the inductively coupled plasma mass spectrometer is used to test the metal element in the carbon fiber sample to be tested, a reasonable pretreatment mode is used to treat the carbon fiber sample and control each condition in the pretreatment process, so that adverse effects of impurities in the sample on the accuracy of the detection result are prevented, and the accuracy and sensitivity of the detection result are ensured.
According to some preferred embodiments, in step (1), the carbon fiber fragments have a particle size of less than 2cm (e.g., may be 2cm, 1.5cm, or 1 cm).
According to some preferred embodiments, in step (2), the calcination is carried out at a temperature of 700 to 750 ℃ (e.g., may be 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃ or 750 ℃) for a time of 10 to 12 hours (e.g., may be 10 hours, 11 hours or 12 hours).
In the embodiment, the carbon fiber sample can be sheared and cut into the carbon fiber fragments with the particle size by using scissors, and then the carbon fiber fragments are calcined to obtain carbon fiber powder, so that the carbon fiber powder can be obtained by combusting in a shorter time, and the earlier treatment time is shorter; meanwhile, in this embodiment, a large number of experiments prove that the calcination temperature and time of the carbon fiber fragments are controlled within the above ranges, so that the accuracy of detection can be ensured, for example, if the calcination temperature is too high, the retention rate of metal elements in the carbon fiber fragments is lower, so that the accuracy of detecting the content of the metal elements in the subsequent carbon fiber samples is adversely affected, and if the calcination temperature is too low, the impurity content in the carbon fiber fragments is more, the calcination time is too long, and the accuracy of detecting the content of the metal elements in the subsequent carbon fiber samples is adversely affected.
When the carbon fiber fragments are calcined, 3 to 5g of the carbon fiber fragments can be firstly weighed into a platinum crucible, put into a muffle constant temperature zone, calcined at the temperature until no obvious black substance exists, taken out of the platinum crucible and cooled to room temperature in a dryer.
According to some preferred embodiments, in step (2), the acid digestion employs an acid solution of perchloric acid and hydrofluoric acid; wherein, the volume ratio of perchloric acid to hydrofluoric acid is 1: (3-4) (e.g., may be 1:3, 1:3.5, or 1:4); the acid digestion is carried out at a temperature of 235-245 ℃ (e.g., 235 ℃, 240 ℃ or 245 ℃) for a time of 1.5-2 hours (e.g., 1.5 hours, 1.8 hours or 2 hours).
In this embodiment, since the carbon fiber fragments contain a certain amount of silicon element, in order to dissolve the carbon fiber powder formed after calcination, a certain proportion of perchloric acid and hydrofluoric acid are required to be used for heating and acid digestion of the carbon fiber powder, so that the solution to be detected is facilitated to be formed and detected subsequently.
Meanwhile, after perchloric acid and hydrofluoric acid are added into carbon fiber powder to dissolve the carbon fiber powder, the carbon fiber powder is placed on an electric heating plate to be heated and digested, and the temperature is raised to drive out the hydrofluoric acid after the perchloric acid white smoke is exhausted, so that the hydrofluoric acid can be effectively prevented from corroding a sample tube adopted when the ICP-MS is adopted to detect a solution to be detected subsequently.
According to some preferred embodiments, in step (3), the mass fraction of nitric acid after sizing is 2%; the temperature of the heated dissolution is 70 to 80 ℃ (for example, it may be 70 ℃, 75 ℃ or 80 ℃) for 5 to 10 minutes (for example, it may be 5 minutes, 8 minutes or 10 minutes).
In this embodiment, after the pretreatment is completed, 2mL of dilute nitric acid (with a mass concentration of 50%) is added into the sample to be detected, and the sample is placed on an electric hot plate for heating, and after cooling, the solution is fixed to a volumetric flask with a volume of 50mL, so as to obtain the solution to be detected.
According to some preferred embodiments, the standard curve equation of each metal element is fitted by:
Preparing a blank solution and a plurality of standard solutions with different concentrations respectively; wherein the standard solution is a solution respectively containing one metal element, and the blank solution is a solution without the metal element; the metal elements are potassium, sodium, calcium, magnesium, iron, aluminum and titanium;
detecting the standard solution and the blank solution under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a second detection result corresponding to the blank solution and a first detection result corresponding to each standard solution;
And fitting to obtain a standard curve equation of each metal element according to each first detection result and the concentration of the metal element in each standard solution.
Because the content of impurity elements such as potassium, sodium, calcium, magnesium, iron, aluminum, titanium and the like in the carbon fiber has a large influence on the oxidation resistance, the content of the metal elements in the carbon fiber is detected mainly by an ICP-MS method in the embodiment, because the carbon fiber contains complex components, the recovery rate of an internal standard is influenced by the content of the internal standard element, and the test result is basically not influenced by an external standard method, so the embodiment adopts the external standard method for detection. Firstly, preparing a plurality of standard solutions with different concentrations, wherein the specific preparation method is as follows: respectively selecting standard stock solutions of potassium, sodium, calcium, magnesium, iron, aluminum and titanium metals, and diluting each metal standard stock solution by using 5% dilute nitric acid to respectively obtain a plurality of standard solutions with different concentration series; and then respectively detecting the standard solutions by utilizing an ICP-MS instrument to respectively obtain mass spectrograms (namely first detection results) of the standard solutions of the metal elements with different concentrations, respectively obtaining peak areas corresponding to the metal elements in the different concentrations from the mass spectrograms of the standard solutions of the metal elements with different concentrations, taking the peak areas of the metal elements obtained in the chromatograms of the standard solutions with each concentration as an ordinate y of a standard curve equation, taking the concentration in the standard working solution of the metal elements as an abscissa x of the standard curve equation, carrying out linear regression on the data with different concentrations obtained by the detection, fitting to obtain a standard curve equation of y=a×x+b, and obtaining weight coefficients a and b, wherein the weight coefficient a is the slope of the standard curve equation, and the weight coefficient b is the intercept of the standard curve equation.
The blank solution was diluted nitric acid with a mass fraction of 2%.
According to some preferred embodiments, the preset test conditions include:
adopting a Helium KED analysis mode;
The radio frequency power is 1600W, the integration time is 1000ms, the temperature of the atomizing chamber is 2 ℃, the flow rate of the plasma gas is 15L/min, the flow rate of the carrier gas is 1.04mL/min, the flow rate of the He gas is 4-5 mL/min (for example, 4mL/min, 4.5mL/min or 5 mL/min), the rotating speed of the peristaltic pump is 35rpm, the lifting rate of the sample is 0.3r/s, and the repetition time is 2-3 times (for example, 2 times or 3 times).
In the embodiment, a large number of experiments prove that the content of the metal element in the carbon fiber sample is detected under the preset test condition, so that when the method in the embodiment of the invention is adopted to detect the carbon fiber, the final detection limit is lower, the sensitivity is higher, the accuracy is higher, the repeatability is better and the application range is wider.
According to some preferred embodiments, the calculating the content of each metal element in the carbon fiber sample according to the standard curve equation of each metal element, the detection result of the blank solution, and the detection result of the solution to be detected includes:
Obtaining the concentration of each metal element in the carbon fiber sample based on the standard curve equation of each metal element and the detection result of the solution to be detected;
And calculating the content of each metal element in the carbon fiber sample according to the concentration of each metal element and the detection result of the blank solution.
According to some preferred embodiments, the content of each metal element in the carbon fiber sample is calculated by the following formula:
Wherein w is the mass fraction of the metal element to be detected in the carbon fiber sample, and the unit is; c is the mass concentration of the detected metal element in the solution to be detected and the mass concentration of the detected metal element in the blank solution, wherein the unit is mug/mL; m is the mass of the carbon fiber fragments, and the unit is g; v is the total volume of the solution to be detected, and the unit is mL; v 1 is the partitioned volume of the solution to be detected, and the unit is mL; v 2 is the test liquid volume of the solution to be tested, in mL.
In order to more clearly illustrate the technical scheme and advantages of the invention, a method for detecting metal elements in carbon fiber impurities is described in detail below through several embodiments.
Example 1:
preparing a solution to be detected of a carbon fiber sample:
(1) Cutting the carbon fiber by scissors to obtain carbon fiber fragments below 2 mm;
(2) Accurately weighing 3-5 g of carbon fiber fragments in a platinum crucible, placing the platinum crucible in a muffle furnace constant temperature area, calcining at 700 ℃ for 12 hours until no obvious black substance exists, taking out the platinum crucible, and placing the platinum crucible in a dryer for cooling to room temperature (25 ℃) to obtain carbon fiber powder; then, 0.5mL of perchloric acid and 2mL of hydrofluoric acid are removed and placed in a platinum crucible, the platinum crucible is placed on an electric heating plate and heated at 240 ℃ for digestion for 2 hours, the hydrofluoric acid is removed after the perchloric acid white smoke is exhausted, and a sample to be detected is obtained after the crucible is cooled;
(3) Adding 2mL of dilute nitric acid (the mass concentration is 50%) into a platinum crucible along the inner wall, heating and dissolving the solution on an electric plate at 80 ℃ for 5-10 min, cooling the solution, and fixing the volume of the solution into a 50mL volumetric flask to obtain the solution to be detected.
Preparing a standard solution:
Selecting standard stock solutions of potassium, sodium, calcium, magnesium, iron, aluminum and titanium metals, respectively diluting the standard stock solutions to standard curve concentrations by using 5% dilute nitric acid to respectively obtain a plurality of standard solutions of different concentration series; potassium metal standard solution: 50 μg/L, 60 μg/L, 80 μg/L, 100 μg/L, 120 μg/L, 150 μg/L; sodium metal standard solution: 120 μg/L, 150 μg/L, 200 μg/L, 500 μg/L, 1000 μg/L, 1500 μg/L; standard calcium metal solution: 20. Mu.g/L, 40. Mu.g/L, 50. Mu.g/L, 60. Mu.g/L, 80. Mu.g/L, 100. Mu.g/L; magnesium metal standard solution: 20. Mu.g/L, 40. Mu.g/L, 50. Mu.g/L, 60. Mu.g/L, 80. Mu.g/L, 100. Mu.g/L; standard solution of iron metal: 20. Mu.g/L, 40. Mu.g/L, 50. Mu.g/L, 60. Mu.g/L, 80. Mu.g/L, 100. Mu.g/L; aluminum metal standard solution: 20. Mu.g/L, 40. Mu.g/L, 50. Mu.g/L, 60. Mu.g/L, 80. Mu.g/L, 100. Mu.g/L; titanium metal standard solution: 20. Mu.g/L, 40. Mu.g/L, 50. Mu.g/L, 60. Mu.g/L, 80. Mu.g/L, 100. Mu.g/L;
Preparing a blank solution: placing a platinum crucible without adding a carbon fiber sample into a muffle furnace constant temperature area, calcining for 12h at 700 ℃, taking out the platinum crucible, and placing the platinum crucible into a dryer to be cooled to room temperature (25 ℃); and then, transferring 0.5mL of perchloric acid and 2mL of hydrofluoric acid into a platinum crucible, then, placing the platinum crucible on an electric plate, heating and digesting for 2 hours at 240 ℃, heating and removing the hydrofluoric acid after the perchloric acid white smoke is exhausted, and adding nitric acid to a constant volume of 50mL after the crucible is cooled to obtain a blank solution.
Standard curve equation fitting:
Detecting standard solutions by utilizing ICP-MS under the test conditions of the table 1 to obtain a mass spectrum corresponding to each standard solution; and respectively obtaining peak areas corresponding to the metal elements in the standard solution under different concentrations of the metal elements from a mass spectrogram of the standard solution, taking the peak areas of the metal elements obtained in the chromatogram of the standard solution with each concentration as an ordinate y of a standard curve equation, taking the concentration in the standard working solution of the metal elements as an abscissa x of the standard curve equation, carrying out linear regression on the data with different concentrations obtained by detection, fitting to obtain a standard curve equation, wherein y=a×x+b, and obtaining weight coefficients a and b, wherein the weight coefficient a is the slope of the standard curve equation, and the weight coefficient b is the intercept of the standard curve equation.
Testing the content of metal elements in a carbon fiber sample:
Detecting the solution to be detected under the test condition of the table 1 by utilizing ICP-MS to obtain a detection result of the solution to be detected; substituting the detection result into a standard curve equation of the metal element to obtain the concentration of each metal element in the carbon fiber sample, and calculating according to the following formula to obtain the content of each metal element in the carbon fiber sample.
Wherein w is the mass fraction of metal elements to be detected in the carbon fiber sample, and the unit is; c is the mass concentration of the detected metal element in the solution to be detected and the mass concentration of the detected metal element in the blank solution, wherein the unit is mug/mL; m is the mass of the carbon fiber fragments, and the unit is g; v is the total volume of the solution to be detected, and the unit is mL; v 1 is the partitioned volume of the solution to be detected, and the unit is mL; v 2 is the test liquid volume of the solution to be tested in mL.
Example 2: sensitivity verification
Under the condition that a carbon fiber sample is not added, a certain amount of standard solution of potassium, sodium, calcium, magnesium, iron, aluminum and titanium elements is added into a blank solution according to the table 2, the test is carried out on the sample under the test condition of the table 1 by using an inductively coupled plasma mass spectrometer, and the sensitivity of the instrument to the potassium, sodium, calcium, magnesium, iron, aluminum and titanium elements is examined, and the test results are shown in the table 2.
TABLE 1
| Parameters (parameters) | Setting value | Parameters (parameters) | Setting value |
| Radio frequency power/W | 1600 | Carrier gas flow rate/(mL/min) | 1.04 |
| Integration time/ms | 1000 | He gas flow rate/(mL/min) | 4 |
| Analysis mode | HeliumKED | Peristaltic pump speed/rpm | 35 |
| Atomizing chamber temperature/°c | 2 | Sample lifting rate/(r/s) | 0.3 |
| Plasma gas flow/(L/min) | 15 | Number of repetitions/time | 3 |
TABLE 2
| Element(s) | K | Na | Ca | Mg | Fe | Al | Ti |
| Concentration of addition mark/(μg/L) | 50.00 | 150.00 | 50.00 | 50.00 | 50.00 | 50.00 | 50.00 |
| Measured concentration/(μg/L) | 48.33 | 152.17 | 52.03 | 48.18 | 51.77 | 48.76 | 50.95 |
| Recovery/% | 96.66 | 101.45 | 104.07 | 96.36 | 103.54 | 97.52 | 101.90 |
As shown in Table 2, the standard recovery rate of potassium, sodium, calcium, magnesium, iron, aluminum and titanium elements is between 96% and 105%, which indicates that the selectivity of instrument parameters is good.
Example 3: precision verification
To verify the precision of the instrument and method test results, the sample injection measurement was repeated 7 times using 50. Mu.g/L concentration points of standard solutions in the standard curve according to the test conditions in Table 1, and the standard deviation was calculated, and the results are shown in Table 3. And analysis and measurement of the sample were performed at short time intervals by using the actual carbon fiber sample to examine the reproducibility of the method, and the results are shown in table 4.
TABLE 3 Table 3
TABLE 4 Table 4
As shown in Table 3, the Relative Standard Deviation (RSD) of each metal element was less than 10%, indicating that the instrument reproducibility was good. As shown in Table 4, the Relative Standard Deviation (RSD) of each test of the samples was less than 10%, demonstrating good reproducibility of the method.
Example 4: accuracy verification
To verify the accuracy of the method, a standard solution of known concentration was added to the solution to be tested, the test was performed under the test conditions shown in table 1, the measured concentration of the sample was subtracted from the actual concentration measured when no analyte was originally added, and the percentage of the added concentration was removed, and the measurement of the labeling recovery rate was performed, and the results are shown in table 5.
TABLE 5
| Element(s) | K | Na | Ca | Mg | Fe | Al | Ti |
| Scalar/(μg/g) | 1.00 | 2.40 | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 |
| Mark recovery/% | 94.86 | 94.45 | 100.95 | 98.00 | 99.15 | 107.98 | 99.48 |
| Scalar/(μg/g) | 1.60 | 100.00 | 1.20 | 1.20 | 1.20 | 0.80 | 1.20 |
| Mark recovery/% | 98.99 | 101.15 | 87.67 | 103.33 | 102.41 | 102.26 | 103.78 |
| Scalar/(μg/g) | 3.00 | 30.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| Mark recovery/% | 101.38 | 100.75 | 98.74 | 98.71 | 98.33 | 98.70 | 98.14 |
As shown in Table 5, the recovery rate data shows that the labeled recovery rate of the elements is maintained at 87% -110%, and the accuracy of the method is good.
Example 5: detection limit and quantitative limit verification
The standard solutions of the low concentration points were added to the blank solutions, followed by measurement for 10 times, calculation of standard deviation, detection of 3-fold standard deviation, and determination of 10-fold standard deviation, and the results are shown in Table 6 below.
TABLE 6
As can be seen from table 6, the detection limit in this example is 3.10×10 -6～9.70*10-6, indicating that the detection limit of the method is low.
Example 5: method applicability verification
Because the carbon fiber contains products such as tows, filaments, short fibers and the like, and the variety of the precursor is many. In order to verify the applicability of the method, 5 different types of carbon fibers are collected in the embodiment, carbon fibers and precursors of specification types such as T700, T800, M40 and the like are covered, different calcining temperatures are adopted to respectively calcine each carbon fiber sample in the pretreatment process, the prepared solution to be detected is used for testing the content of metal elements in the samples by utilizing ICP-MS according to the testing conditions in Table 1,
The results are shown in Table 7.
TABLE 7
In the calcination process of different carbon fiber samples, the higher the temperature is, the faster the combustion speed is, but a certain amount of alkali metal and alkaline earth metal may volatilize, so that the measurement result is lower. However, if the calcination temperature is too low, the combustion time is long, and when the calcination temperature is 600 ℃, the 5g carbon fiber sample is burned into the weighted ash for more than 15 hours, which is inconvenient for rapidly measuring the element content in the carbon fiber.
Meanwhile, as can be seen from Table 7, the measured values of the respective metal elements in the different samples are close in the temperature range of 600 to 700 ℃, but as the temperature increases again, the content of the respective metal elements in the carbon fiber sample is significantly reduced, especially the content of potassium element, and the content of part of the sample is less than 30% of the original content, which is related to the potassium boiling point of 774 ℃, the iron boiling point is 2800 ℃, the aluminum boiling point is 2500 ℃, the titanium boiling point is 3300 ℃, and the contents of iron, aluminum and titanium are not greatly changed in the range of 600 to 900 ℃. In the present invention, the calcination temperature in the carbon fiber sample is determined to be 700 to 750 ℃.
In conclusion, the detection method of the metal element in the carbon fiber impurity provided by the invention has the advantages of high sensitivity, low detection limit, multiple types of detected metal elements, high precision, good accuracy and wide application range.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The method for detecting the metal element in the carbon fiber impurity is characterized by comprising the following steps of:
pretreating a carbon fiber sample, and preparing the carbon fiber sample into a solution to obtain a solution to be detected of the carbon fiber sample;
Detecting the solution to be detected under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a detection result of the solution to be detected;
Calculating the content of each metal element in the carbon fiber sample according to a standard curve equation of each metal element, a detection result of a blank solution and a detection result of the solution to be detected; the standard curve equation of each metal element is obtained by fitting a first detection result of a standard solution containing each metal element at a plurality of different concentrations and the concentration of the metal element in each standard solution.
2. The method according to claim 1, wherein the method for preparing the solution to be detected comprises:
(1) Cutting the carbon fiber sample to obtain carbon fiber fragments;
(2) Calcining and acid digestion are sequentially carried out on the carbon fiber fragments to obtain a sample to be detected;
(3) Adding nitric acid into the sample to be detected, heating for dissolving and fixing the volume to obtain the solution to be detected.
3. The method according to claim 2, wherein in the step (1), the particle size of the carbon fiber fragments is less than 2cm.
4. The method according to claim 2, wherein in the step (2), the calcination is performed at a temperature of 700 to 750 ℃ for a time of 10 to 12 hours.
5. The method according to claim 2, wherein in the step (2), the acid digestion uses an acid solution of perchloric acid and hydrofluoric acid; wherein, the volume ratio of perchloric acid to hydrofluoric acid is 1: (3-4);
the temperature of the acid digestion is 235-245 ℃ and the time is 1.5-2 h.
6. The method according to claim 2, wherein in the step (3), the temperature of the heating dissolution is 70 to 80 ℃ for 5 to 10 minutes.
7. The method according to claim 1, wherein the standard curve equation of each metal element is fitted by:
Preparing a blank solution and a plurality of standard solutions with different concentrations respectively; wherein the standard solution is a solution respectively containing one metal element, and the blank solution is a solution without the metal element; the metal elements are potassium, sodium, calcium, magnesium, iron, aluminum and titanium;
detecting the standard solution and the blank solution under a preset test condition by using an inductively coupled plasma mass spectrometer to obtain a second detection result corresponding to the blank solution and a first detection result corresponding to each standard solution;
And fitting to obtain a standard curve equation of each metal element according to each first detection result and the concentration of the metal element in each standard solution.
8. The method according to claim 1, wherein the predetermined test conditions include:
adopting a Helium KED analysis mode;
The radio frequency power is 1600W, the integration time is 1000ms, the temperature of an atomization chamber is 2 ℃, the flow rate of plasma gas is 15L/min, the flow rate of carrier gas is 1.04mL/min, the flow rate of He gas is 4-5 mL/min, the rotating speed of a peristaltic pump is 35rpm, the lifting rate of a sample is 0.3r/s, and the repetition times are 2-3 times.
9. The method according to any one of claims 1 to 8, wherein the calculating the content of each metal element in the carbon fiber sample based on the standard curve equation of each metal element, the detection result of the blank solution, and the detection result of the solution to be detected includes:
Obtaining the concentration of each metal element in the carbon fiber sample based on the standard curve equation of each metal element and the detection result of the solution to be detected;
And calculating the content of each metal element in the carbon fiber sample according to the concentration of each metal element and the detection result of the blank solution.
10. The method according to claim 9, wherein the content of each metal element in the carbon fiber sample is calculated by the following formula:
wherein w is the mass fraction of the metal element to be detected in the carbon fiber sample, and the unit is; c is the mass concentration of the detected metal element in the solution to be detected and the mass concentration of the detected metal element in the blank solution, wherein the unit is mug/mL; m is the mass of the carbon fiber fragments, and the unit is g; v is
The total volume of the solution to be detected is in mL; v 1 is the partitioned volume of the solution to be detected,
The unit is mL; v 2 is the test liquid volume of the solution to be tested, in mL.
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