CN110361441B - Method for detecting trace impurity elements in tungsten carbide powder - Google Patents
Method for detecting trace impurity elements in tungsten carbide powder Download PDFInfo
- Publication number
- CN110361441B CN110361441B CN201910469001.3A CN201910469001A CN110361441B CN 110361441 B CN110361441 B CN 110361441B CN 201910469001 A CN201910469001 A CN 201910469001A CN 110361441 B CN110361441 B CN 110361441B
- Authority
- CN
- China
- Prior art keywords
- solution
- mixed
- tungsten carbide
- impurity elements
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- G01N1/40—Concentrating samples
- G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
-
- 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
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- 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
Landscapes
- 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)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for detecting trace impurity elements in tungsten carbide powder, which specifically adopts an inductively coupled plasma mass spectrometry method to simultaneously and rapidly detect eighteen impurity elements such as magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth and the like, wherein the lower limit of the detection of the impurity elements is less than 0.0001 percent. According to the method, a tungsten carbide sample is oxidized into tungsten trioxide in a high-temperature furnace, and then the sample is digested by ammonia water, so that the problem of interference of a large amount of insoluble free carbon during wet decomposition of tungsten carbide is effectively solved, a tungsten matrix matching working curve is adopted to eliminate a matrix inhibition effect, and the measurement is carried out by an inductively coupled plasma mass spectrometer. The method has the advantages of simple operation, more detection elements, high detection speed, low lower limit of measurement, trace level achievement and high analysis accuracy, and is suitable for batch production analysis of high-quality or high-purity tungsten carbide.
Description
Technical Field
The invention relates to the technical field of analysis of trace impurity elements of high-purity materials, in particular to a method for detecting trace impurity elements in tungsten carbide powder, and specifically relates to a method for measuring the content of eighteen impurity elements such as magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead and bismuth in the tungsten carbide powder by adopting an inductively coupled plasma mass spectrometer.
Background
The tungsten carbide powder is used as a main raw material for producing the hard alloy, wherein the content of impurity elements is an important index for controlling the quality of the hard alloy product. At present, the detection standards of the content of trace impurity elements in tungsten carbide powder are as follows: the method comprises the following steps of an industry standard YS/T559-2009 and a national standard GB/T4324.1-30-2012.
YS/T559-2009 tungsten emission spectrum analysis method is direct current arc atomic emission spectrometry. The method needs spectrum shooting, measures blackness, has complicated analysis steps, and establishes a working curve depending on a solid standard sample, and the lower analysis limit cannot meet the detection requirement of high-purity tungsten carbide;
the series of standards of GB/T4324.1-30-2012 tungsten chemical analysis methods are single element determination methods, the analysis efficiency is low, and the requirements of multi-element rapid analysis cannot be met.
The reports of the analysis of impurity elements in the tungsten carbide powder are few, and most of the reports are the analysis of high-content doping elements in the doped tungsten carbide. The analysis documents of trace impurity elements in the tungsten carbide powder are as follows:
CN103257136A Chinese patent discloses a method for measuring calcium, cobalt, chromium and iron elements in tungsten carbide, which is to analyze 4 elements in WC-Co10-Cr4 tungsten carbide high-temperature alloy, wherein the content of cobalt and chromium is more than 1 percent, and the method does not belong to trace element analysis;
CN105823772A, the chinese patent discloses "a method for detecting impurity elements in tungsten carbide", which is a method for detecting the amount of cobalt, nickel, iron, titanium, aluminum, manganese, magnesium, vanadium, chromium, copper and molybdenum in tungsten carbide and cast tungsten carbide by using inductively coupled plasma atomic emission spectrometry, wherein the method uses hydrofluoric acid, nitric acid and other strong acids to digest samples, which can not digest free carbon in tungsten carbide, and can not accurately detect elements less than 0.0001%;
the CN103529015A Chinese patent discloses a method for analyzing and detecting cobalt, nickel, iron, titanium and chromium in tungsten carbide, which is to dissolve a tungsten carbide sample by sulfuric acid-ammonium sulfate and complex tungsten by citric acid, and is not suitable for measuring trace impurities due to high reagent blank.
"Standard addition atomic absorption method for measuring the content of trace Fe, Mg, Ca, K and Na in tungsten carbide" published in proceedings of the institute of advanced cigarette arts (Nature science edition) 2001, volume 17, 266 and 269, wherein the method adopts atomic absorption spectrometry and single element measurement, and the content of elements to be measured is more than 0.01%;
the modern instrument, 40-41 pages 05 of 1999, discloses that the method for measuring the trace arsenic in the tungsten carbide and the compound thereof adopts a hydrogenation separation pretreatment spectrophotometry method to measure the trace arsenic, and is a single element measurement.
Inductively coupled plasma mass spectrometry (ICP-MS) is an advanced technology for trace element analysis research and application, has the advantages of high sensitivity, low detection limit, less spectral line interference, simultaneous determination of multiple elements and the like, is widely applied to determination of trace elements in high-purity materials, but has no relevant report on analysis of trace impurity elements in high-purity tungsten carbide. Reports of using inductively coupled plasma mass spectrometry to determine impurity elements in high-purity tungsten include:
4% H is adopted in the method for determining phosphorus and other trace elements in high-purity ammonium paratungstate by using inductively coupled plasma mass spectrometry, which is disclosed in analytical chemistry 2009, 03, 403, 406 2 O 2 Ammonium paratungstate is digested, and tungsten carbide cannot be digested;
research on ICP-MS (inductively coupled plasma-mass spectrometry) method for measuring impurities in pure tungsten products, disclosed in 2009, 24, vol.01, page 43-46, by using H 2 O 2 Digesting the tungsten product, wherein tungsten carbide cannot be completely dissolved to be clear;
in the method, 15 trace impurity elements in high-purity tungsten are measured by an inductively coupled plasma mass spectrometry method in the 4 th stage of volume 32 of 7 month in 2011, tungsten powder and a tungsten bar sample are dissolved by hydrofluoric acid-nitric acid, the tungsten carbide powder cannot be completely digested, an internal standard is required to be added for compensating a matrix effect, and trace impurity elements are easily introduced;
h is used in the method for determining trace metal impurities in high-purity tungsten powder by using an ion chromatography-membrane desolventizing-ICP-MS method disclosed in analytical laboratory 2009, volume 28, No. 1, page 104-106 2 O 2 After dissolving the metal tungsten powder, separating the tungsten matrix by cation exchange of ion chromatography, and carrying out ICP-MS measurement after atomizing by a membrane desolventizing device. The analysis device is complex and not suitable for tungsten carbide samples;
h is adopted for determining 26 trace impurity elements in high-purity tungsten by inductively coupled plasma mass spectrometry as disclosed in hard alloy 2014, volume 31, page 05, 309 and 314 2 O 2 The high-purity tungsten sample is dissolved, and the tungsten carbide cannot be completely dissolved.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting more than ten trace impurity elements in tungsten carbide, which has high sample dissolving efficiency, low analysis lower limit and simple and convenient operation.
The method effectively solves the problem of the digestion of the tungsten carbide powder by oxidation decarbonization, adopts the tungsten matrix matching standard solution to draw a working curve to eliminate the serious matrix inhibition effect, does not separate the tungsten matrix, does not need to add internal standard elements, adopts the inductively coupled plasma mass spectrometry to simultaneously determine eighteen trace impurity elements in the tungsten carbide, and has the determination lower limit of 0.019 mu g/g to 1.1 mu g/g. The method is accurate, reliable, simple, convenient and quick, and can realize quick and batch detection of the high-purity tungsten carbide powder.
The method for detecting trace impurity elements in the tungsten carbide powder comprises the following steps:
step one, oxidizing a tungsten carbide sample to obtain an oxidized sample;
secondly, digesting the oxidized sample with ammonia water to obtain a digestion solution;
and step three, obtaining the content of the trace impurity elements in the digestion solution.
In some embodiments of the invention, the third step comprises a step of determining the content of the impurity element in the digestion solution by using an inductively coupled plasma mass spectrometer.
In some embodiments of the invention, in the first step, the temperature for oxidizing the tungsten carbide sample is 600-800 ℃, and the time for oxidizing is 5-20 min.
In some embodiments of the invention, in the second step, the volume-to-mass ratio of the amount of the ammonia water to the amount of the tungsten carbide sample is 10-20 mL:1 g.
In some embodiments of the invention, in the second step, a low-temperature heating step is further included in the process of digesting the oxidized sample with ammonia water.
In some embodiments of the present invention, in the low-temperature heating step in the second step, the low-temperature heating temperature is 100 to 150 ℃.
In some embodiments of the invention, the mass to volume dilution ratio between the mass of the tungsten carbide sample and the volume of the resulting digestion solution in step one is 1 g: 1000 mL-10000 mL.
In some embodiments of the invention, the trace impurity elements are selected from one or more, preferably eighteen, trace impurity elements selected from magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, and bismuth.
In some embodiments of the present invention, the third step comprises:
step three (1), preparing a series of standard solutions: digesting a high-purity tungsten substrate, and respectively adding solutions of impurity elements with different amounts to form impurity element series concentrations; preferably, the high-purity tungsten substrate is ammonium paratungstate or tungsten powder; preferably, the process of digesting the high-purity tungsten matrix by using the ammonia water further comprises a low-temperature heating step; preferably, in the low-temperature heating step, the heating temperature is 100-150 ℃;
thirdly, determining a digestion solution and a series of standard samples of the tungsten carbide sample by adopting an inductively coupled plasma mass spectrometer; preferably, before measurement, a mixed tuning solution is used for optimizing measurement working parameters of an inductively coupled plasma mass spectrometer, so that the interference of oxide ions is less than 1.5%, and the interference of double-charge ions is less than 3%;
and step three (3), establishing a working curve and calculating the content of impurity elements in the sample.
In some embodiments of the invention, the mixed tuning solution comprises lithium, yttrium, cerium, thallium, cobalt, the medium is nitric acid; preferably, the mass volume concentrations of lithium, yttrium, cerium, thallium and cobalt in the mixed tuning solution are all 5-15ng/mL, preferably 10ng/mL, and the medium is 1.5-2.5%, preferably 2% of nitric acid in volume fraction.
In some embodiments of the invention, the solution containing trace impurity elements comprises a mixed solution 1 containing calcium, molybdenum and lead and a mixed solution 2 containing aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium; preferably, the mass volume concentrations of calcium, molybdenum and lead in the mixed solution 1 are all 0.5-1.5 mug/mL, preferably 1 mug/mL, the medium is nitric acid with 2.0-3.0%, preferably 2.5% volume fraction, the mass volume concentrations of aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium in the mixed solution 2 are all 0.5-1.5 mug/mL, preferably 1 mug/mL, and the medium is nitric acid with 2.0-3.0%, preferably 2.5% volume fraction; more preferably, the mixed solution 1 is prepared by diluting a mixed standard solution A, the mass volume concentrations of calcium, molybdenum and lead in the mixed standard solution A are 40-60 μ g/mL, preferably 50 μ g/mL, the medium is 2.0-3.0%, preferably 2.5% of nitric acid by volume fraction, the mixed solution 2 is prepared by diluting a mixed standard solution B, the mass volume concentrations of aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium in the mixed standard solution B are 80-120 μ g/mL, preferably 100 μ g/mL, the medium is 2.0-3.0mol/L, preferably 2.5mol/L hydrochloric acid, trace nitric acid and hydrofluoric acid (still more preferably, the mixed standard solution A and the mixed standard solution B are both prepared by a single element standard storage solution, the single-element standard storage solution is prepared by respectively using reference substances, and the mass volume concentration of elements in the single-element standard storage solution is 800-.
In some embodiments of the invention, the operating conditions of the inductively coupled plasma mass spectrometer are: the emission power is 900-1300W, the sampling depth is 8.4-16.8 mm, the carrier gas flow is 0.75-0.93L/min, the compensation gas flow is 0.21-0.68L/min, the integration time is 0.3-1 sec, 3-point peak measurement is carried out, and the measurement times are 3 times.
In some embodiments of the invention, aqueous ammonia (ρ 0.90g/mL), MOS grade or high purity; the water for analysis is ultrapure water (not less than 18.3M omega cm) or secondary distilled water.
In some embodiments of the invention, 0.1-0.5 g of a tungsten carbide sample is weighed, placed in an 80-150 mL beaker, and completely oxidized in a muffle furnace. And cooling, adding 10mL of water and 1-10 mL of ammonia water, and heating at low temperature to dissolve the mixture. The mixture is taken down and moved into a volumetric flask after being slightly cooled, and the solution is diluted to 20mL by water and is mixed evenly. Transferring 1000 mu L of test solution into a volumetric flask, diluting to 50mL with water, mixing uniformly, and testing. A reagent blank was made along with the sample. Weighing a high-purity tungsten matrix (omega is more than or equal to 99.999%) with the tungsten amount equivalent to that of a tungsten carbide sample, adding 25mL of water and 1-10 mL of ammonia water, heating at low temperature for dissolving, and steaming to about 15 mL. The solution was transferred to a volumetric flask with a little cooling, diluted to 20mL with water and mixed well. Transferring 1mL of high-purity tungsten matrix sample solution into 5 volumetric flasks with 50mL, respectively adding 0-300 mu L of the mixed solution 1 and the mixed solution 2, diluting with water to a scale, and uniformly mixing. The preparation method of the mixed standard solution A and the mixed standard solution B is formed by respectively diluting and mixing single-standard storage solutions of each element in groups; the nitric acid, hydrofluoric acid and hydrochloric acid are MOS grade or high-purity reagents. The oxidation temperature is 600-800 ℃; the oxidation time is 5-20 min; the low-temperature heating temperature is 100-150 ℃.
The lower limit (10 sigma) of the measurement of eighteen impurity elements in the tungsten carbide by the inductively coupled plasma mass spectrometer is 0.019 mu g/g-1.1 mu g/g.
The invention has the beneficial effects that:
the invention provides a method for analyzing eighteen trace impurity elements in tungsten carbide, aiming at the problems of few analysis elements, high lower analysis limit and poor analysis precision below 0.0010% in the existing detection method. The method solves the problem that a large amount of insoluble free carbon interferes with the determination during the wet decomposition of the tungsten carbide, solves the problem that a tungsten carbide sample is difficult to resolve, resolves the types and the using amount of reagents, eliminates the mass spectrum interference by optimizing and selecting the optimal isotope of the element to be detected, eliminates the tungsten matrix inhibition effect by adopting the tungsten matrix matching working curve, has a plurality of detection elements, high detection speed, low determination lower limit, reaches the trace level, has high analysis accuracy, and is suitable for the batch production analysis of high-quality or high-purity tungsten carbide. The method is simple to operate, rapid in measurement, accurate and reliable in result, and capable of meeting the requirements of scientific research and production.
The invention provides a method for rapidly detecting dozens of trace impurity elements in tungsten carbide powder, which has the technical advantages that:
a. the method solves the problem that the free carbon in the tungsten carbide powder interferes with sample injection measurement, removes the free carbon after oxidizing the sample, and has high oxidation speed and simple operation.
b. The consumption of the digestion reagent is less, strong corrosive reagents such as nitric acid, hydrofluoric acid, hydrogen peroxide and the like are not used, and the digestion method is simple, economic and environment-friendly.
c. The sample does not need to separate a tungsten matrix and does not need internal standard correction, the high-purity tungsten matrix is matched with a standard solution to eliminate the matrix effect, the working condition of the instrument is optimized to reduce the interference of mass spectrum, and the analysis accuracy is high.
d. The method can simultaneously determine the content of eighteen impurity elements in the tungsten carbide, has more analysis elements, high analysis speed and low analysis lower limit, and reaches ng/g level.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Example 1
And (3) determining the content of eighteen impurity elements, namely magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead and bismuth in the 02-type superfine tungsten carbide powder sample.
(1) Preparation of reagents and Standard solutions
Ammonia water (rho 0.90g/mL), MOS grade;
the water for analysis is ultrapure water (not less than 18.3M omega cm);
eighteen impurity element single element standard storage solutions: 1000. mu.g/mL, prepared from the reference substance respectively.
Mixing a standard solution A: calcium, molybdenum and lead are contained, the mass volume concentration is 50 mug/mL, and the medium is 2.5% nitric acid (volume fraction).
Mixing standard solution 1: calcium, molybdenum and lead are contained in the solution 1 mug/mL, the medium is 2.5 percent nitric acid, and the solution is diluted by mixed standard solution A.
Mixing the standard solution B: the medium contains aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium, the mass volume concentration is 100 mu g/mL, the medium contains 2.5mol/L hydrochloric acid, trace nitric acid and hydrofluoric acid, and the trace nitric acid and the hydrofluoric acid are taken as the medium and are brought in when the single-standard medium is diluted.
Mixing standard solution 2: aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium are contained in the mixed standard solution B, the concentration of the mixed standard solution B is 1 mu g/mL, the medium is 2.5% nitric acid (volume fraction), and the mixed standard solution B is diluted to obtain the mixed standard solution.
Lithium, yttrium, cerium, thallium and cobalt mixed tuning liquid: 10ng/mL, medium 2% nitric acid (volume fraction).
(2) Digestion of samples
A0.25 g sample of tungsten carbide was weighed into a 100mL beaker and oxidized in a muffle furnace at 750 ℃ for 10 min. The mixture is cooled down and then is cooled down,
10mL of water and 6mL of ammonia water were added and heated on a 120 ℃ hot plate to dissolve the precipitate. Taking down, cooling for 2-5 min, and immediately moving
Put into a volumetric flask, dilute the solution to 20mL with water and mix well. Transferring 1000 μ L of the test solution into a volumetric flask, and diluting with water to obtain a solution
50mL, mixing evenly and testing. A reagent blank was prepared along with the sample.
(3) Preparing working curve series standard solution
Weighing a high-purity ammonium paratungstate matrix (omega is more than or equal to 99.999 percent) with the tungsten amount equivalent to that of a tungsten carbide sample, adding 25mL of water and 6mL of ammonia water, heating at low temperature for dissolving, and steaming to about 15 mL. The solution was transferred to a volumetric flask with a little cooling, diluted to 20mL with water and mixed well. Transferring 1mL of high-purity tungsten matrix sample solution into 5 volumetric flasks with 50mL, respectively adding 0-300 mu L of mixed standard solution 1 and mixed standard solution 2, diluting with water to a scale, and uniformly mixing.
(4) Measurement of
The mixed tuning solution is used to optimize the working parameters of the instrument, so that the interference of oxide ions is less than 1.5 percent, and the interference of double-charge ions is less than 3 percent. The isotopes of the impurity elements are selected as follows: 24 Mg、 27 Al、 40 Ca、 48 Ti、 51 V、 52 Cr、 55 Mn、 56 Fe、 59 Co、 60 Ni、 63 Cu、 75 As、 95 Mo、 114 Cd、 120 Sn、 121 Sb、 208 Pb、 209 Bi。
and simultaneously measuring the test solution, the reagent blank and the series of standard solutions on the inductively coupled plasma mass spectrometer, drawing a working curve and calculating a result.
The time from oxidation to complete digestion of the tungsten carbide sample in this example was 30 min. The results of detecting eighteen impurity elements in the tungsten carbide sample of this example are shown in table 1:
table 1 test results of example 1
Example 2
Eighteen impurity elements such as magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth and the like in a 06 type tungsten carbide powder sample are measured, and precision measurement is performed.
(1) Preparation of reagents and Standard solutions
Ammonia water (rho 0.90g/mL) with high purity;
redistilled water (not less than 18.3M omega cm) for analysis;
the same procedure as in example 1 is as follows.
(2) Digestion of samples
A0.5 g sample of tungsten carbide was weighed into a 100mL beaker and oxidized in a muffle furnace at 700 ℃ for 12 min. After cooling, 10mL of water and 10mL of ammonia water were added and heated on a hot plate at 150 ℃ to dissolve the mixture. The solution was transferred to a volumetric flask with a little cooling, diluted to 20mL with water and mixed well. Transferring 1000 mu L of test solution into a volumetric flask, diluting to 50mL with water, mixing uniformly, and testing. A reagent blank was prepared along with the sample.
(3) Preparing working curve series standard solution
The same as in example 1.
(4) Measurement of
The same as in example 1.
Precision testing of samples
The test solution was repeatedly measured on an inductively coupled plasma mass spectrometer 11 times, a method precision test was performed, and a measured average value and a Relative Standard Deviation (RSD) were calculated. The results are shown in Table 2.
Table 2 results of duplicate measurements of example 2
Example 3
Eighteen impurity elements such as magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth and the like in a 02-type tungsten carbide powder sample are measured, and are compared with the result measured by a direct current arc Atomic Emission Spectrometry (AES).
(1) Preparation of reagents and Standard solutions
The same as in example 1.
(2) Digestion of samples
A0.1 g sample of tungsten carbide was weighed, placed in a crucible and oxidized in a muffle furnace at 800 ℃ for 15 min. After cooling, 10mL of water and 1mL of ammonia water were added and heated on a hot plate at 100 ℃ to dissolve the precipitate. The solution was transferred to a volumetric flask with a little cooling, diluted to 20mL with water and mixed well. Transferring 10mL of test solution into a volumetric flask, diluting with water to 100mL, mixing uniformly, and testing. A reagent blank was prepared along with the sample.
(3) Preparing working curve series standard solution
The same as in example 1.
(4) Measurement of
The same as in example 1.
The ICP-MS measurement results were compared with those obtained by direct current Arc atomic emission spectrometry (Arc-AES), and are shown in Table 3.
Table 3 example 3 measurement of comparative results
As seen from the table above, the results of measuring seventeen impurity elements by ICP-MS and Arc-AES are completely consistent, the working curve of the Arc-AES solid standard sample has no cadmium, the cadmium cannot be measured, and 12 elements in the Arc-AES solid standard sample cannot be accurately quantified by the Arc-AES, and only less than results can be reported.
Example 4
Meanwhile, eighteen impurity elements such as magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth and the like in a 06 type tungsten carbide powder sample and a tungsten trioxide sample are measured, and standard sample comparison is carried out.
(1) Preparation of reagents and Standard solutions
The same as in example 1.
(2) Digestion of samples
The same as in example 2.
0.59g of tungsten trioxide standard sample is weighed and placed in a 100mL beaker, 8mL of ammonia water is added, and the mixture is heated on an electric hot plate at 150 ℃ to be dissolved and cleared. The mixture is taken down and moved into a volumetric flask after being slightly cooled, and the solution is diluted to 20mL by water and is mixed evenly. Transferring 1000 mu L of test solution into a volumetric flask, diluting to 50mL with water, mixing uniformly, and testing. A reagent blank was prepared along with the sample.
(3) Preparing working curve series standard solution
The same as in example 1.
(4) Measurement of
The same as in example 1.
Table 4 units of measured values and standard values for example 4 and standards: (μ g/g)
The inductively coupled plasma mass spectrometry is used for simultaneously measuring the tungsten carbide sample and the tungsten trioxide standard sample, the result is shown in table 4, the measured value of the standard sample is highly consistent with the standard value, and the method is high in accuracy.
Example 5
And (3) measuring the blank solution of the working curve of the high-purity tungsten matrix for 11 times, and determining the lower limit of eighteen impurity elements such as magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth and the like.
(1) Preparation of reagents and Standard solutions
The same as in example 1.
(2) Preparing working curve series standard solution
The same as in example 1.
(3) Measurement of
The mixed tuning solution is used to optimize the working parameters of the instrument, so that the interference of oxide ions is less than 1.5 percent, and the interference of double-charge ions is less than 3 percent. Measuring on an inductively coupled plasma mass spectrometer, and drawing a working curve. And continuously measuring the matrix blank solution in the standard solution series for 11 times under the selected experimental working conditions, and calculating the standard deviation sigma of the measured values of the impurity elements in the blank solution, wherein 10 sigma is the lower limit of the method measurement. The results are shown in Table 5.
TABLE 5 method determination lower limits for eighteen impurity elements
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (26)
1. A method for detecting trace impurity elements in tungsten carbide powder comprises the following steps:
step one, oxidizing a tungsten carbide sample to obtain an oxidized sample;
secondly, digesting the oxidized sample by ammonia water to obtain a digestion solution;
step three, obtaining the content of impurity elements in the digestion solution;
the third step comprises:
step three (1), preparing a series of standard solutions: digesting a high-purity tungsten substrate, and respectively adding solutions of impurity elements with different amounts to form impurity element series concentrations;
step three (2), determining a digestion solution and a series of standard solutions of the tungsten carbide sample by adopting an inductively coupled plasma mass spectrometer; before measurement, a mixed tuning solution is used for optimizing measurement working parameters of an inductively coupled plasma mass spectrometer, so that the interference of oxide ions is less than 1.5%, and the interference of double-charge ions is less than 3%;
step three (3), establishing a working curve and calculating the content of impurity elements in the sample;
the volume-mass ratio of the amount of the ammonia water to the amount of the tungsten carbide sample is 10-20 mL:1g, and the mass concentration of the ammonia water is 0.90 g/mL;
the process of digesting and oxidizing the sample by ammonia water also comprises a low-temperature heating step, wherein in the low-temperature heating step, the heating temperature is 100-150 ℃;
the mass-volume dilution ratio between the mass of the tungsten carbide sample in the first step and the volume of the digestion solution in the second step is 1 g: 1000 mL-10000 mL.
2. The method according to claim 1, wherein in the first step, the tungsten carbide sample is oxidized at a temperature of 600-800 ℃ for 5-20 min.
3. The method of claim 1, wherein the trace impurity elements are selected from one or more of the eighteen trace impurity elements of magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, and bismuth.
4. The method of claim 2, wherein the trace impurity elements are magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, and bismuth.
5. The method of claim 1, wherein the high purity tungsten substrate is ammonium paratungstate or tungsten powder.
6. The method as claimed in claim 1, wherein the process of digesting the high-purity tungsten matrix by ammonia water further comprises a low-temperature heating step.
7. The method according to claim 6, wherein the low-temperature heating step is performed at a temperature of 100 to 150 ℃.
8. The method of claim 1, wherein the mixed tuning solution comprises lithium, yttrium, cerium, thallium, and cobalt, and the medium is nitric acid.
9. The method as claimed in claim 8, wherein the mass volume concentrations of lithium, yttrium, cerium, thallium and cobalt in the mixed tuning solution are all 5-15ng/mL, and the volume fraction of the medium is 1-1.5%.
10. The method of claim 9, wherein the mixed tuning solution has a mass volume concentration of lithium, yttrium, cerium, thallium, and cobalt of 10 ng/mL.
11. The method of claim 9, wherein the medium is 2% volume fraction nitric acid.
12. The method according to claim 1, wherein the impurity element-containing solution includes a mixed solution 1 containing calcium, molybdenum, and lead, and a mixed solution 2 containing aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium, and vanadium.
13. The method according to claim 12, wherein the mass volume concentrations of calcium, molybdenum and lead in the mixed solution 1 are all 0.5-1.5 μ g/mL, the volume fraction of the medium is 2.0-3.0%, the mass volume concentrations of aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium in the mixed solution 2 are all 0.5-1.5 μ g/mL, and the volume fraction of the medium is 2.0-3.0%.
14. The method according to claim 13, wherein the mass-volume concentrations of calcium, molybdenum and lead in the mixed solution 1 are all 1 μ g/mL.
15. The method of claim 13 wherein the medium in mixed liquor 1 is 2.5% volume fraction nitric acid.
16. The method according to claim 13, wherein the mass volume concentrations of aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium in the mixed solution 2 are all 1 μ g/mL.
17. The method of claim 13 wherein the medium in mixed liquor 2 is 2.5% volume fraction nitric acid.
18. The method according to claim 13, wherein the mixed solution 1 is prepared by diluting a mixed standard solution A, the mass volume concentrations of calcium, molybdenum and lead in the mixed standard solution A are all 40-60 μ g/mL, and the volume fraction of the medium is 2.0-3.0%; the mixed solution 2 is formed by diluting a mixed standard solution B, the mass volume concentration of aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium in the mixed standard solution B is 80-120 mu g/mL, and the volume fraction of a medium is 2.0-3.0 mol/L.
19. The method according to claim 18, wherein the mass volume concentrations of calcium, molybdenum and lead in the mixed standard solution A are all 50 μ g/mL.
20. The method of claim 18, wherein the medium of the mixed standard solution a is 2.5% volume fraction nitric acid.
21. The method according to claim 18, wherein the mass volume concentrations of aluminum, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium in the mixed standard solution B are all 100 μ g/mL.
22. The method according to claim 18, wherein the medium in the mixed standard solution B is 2.5mol/L hydrochloric acid, trace nitric acid and hydrofluoric acid.
23. The method as claimed in claim 18, wherein the mixed standard solution A and the mixed standard solution B are both prepared from single element standard storage solutions, the single element standard storage solutions are respectively prepared from reference substances, and the mass volume concentration of elements in the single element standard storage solution is 800-1200 μ g/mL.
24. The method of claim 23, wherein the mass volume concentration of the element in the single-element standard storage solution is 1000 μ g/mL.
25. The method of claim 1, wherein the inductively coupled plasma mass spectrometer is operated under the following conditions: the emission power is 900-1300W, the sampling depth is 8.4-16.8 mm, the carrier gas flow is 0.75-0.93L/min, the compensation gas flow is 0.21-0.68L/min, the integration time is 0.3-1 sec, 3-point peak measurement is carried out, and the measurement times are 2-4 times.
26. The method of claim 25, wherein the number of measurements is 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910469001.3A CN110361441B (en) | 2019-05-31 | 2019-05-31 | Method for detecting trace impurity elements in tungsten carbide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910469001.3A CN110361441B (en) | 2019-05-31 | 2019-05-31 | Method for detecting trace impurity elements in tungsten carbide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110361441A CN110361441A (en) | 2019-10-22 |
| CN110361441B true CN110361441B (en) | 2022-09-09 |
Family
ID=68215417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910469001.3A Active CN110361441B (en) | 2019-05-31 | 2019-05-31 | Method for detecting trace impurity elements in tungsten carbide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110361441B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112730591B (en) * | 2021-01-25 | 2023-12-22 | 云南临沧鑫圆锗业股份有限公司 | Sampling and testing method for measuring content of trace impurity elements in high-purity germanium tetrafluoride |
| CN113390860A (en) * | 2021-06-29 | 2021-09-14 | 洛阳金鹭硬质合金工具有限公司 | Detection method for simultaneously detecting sixteen trace impurity elements in chromium carbide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230861A (en) * | 2011-03-30 | 2011-11-02 | 攀钢集团有限公司 | Method of digesting, settling and separating tungsten-based samples and detection method for tungsten-based samples |
| CN102854179A (en) * | 2012-10-11 | 2013-01-02 | 株洲硬质合金集团有限公司 | Method for analyzing and detecting cadmium impurity element in tungsten or tungsten compound |
-
2019
- 2019-05-31 CN CN201910469001.3A patent/CN110361441B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230861A (en) * | 2011-03-30 | 2011-11-02 | 攀钢集团有限公司 | Method of digesting, settling and separating tungsten-based samples and detection method for tungsten-based samples |
| CN102854179A (en) * | 2012-10-11 | 2013-01-02 | 株洲硬质合金集团有限公司 | Method for analyzing and detecting cadmium impurity element in tungsten or tungsten compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110361441A (en) | 2019-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110514643B (en) | Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry | |
| KR20120085296A (en) | Method for analyzing and detecting calcium element in ore | |
| CN107121426B (en) | Clear up the method for vanadium chromium titanium alloy and the detection method of digestion solution | |
| CN103604800A (en) | Analysis method for determining titanium, vanadium, tungsten, manganese and silicon in K25 chromium-base high temperature alloy | |
| CN110361441B (en) | Method for detecting trace impurity elements in tungsten carbide powder | |
| CN102680470B (en) | Method for determining content of arsenic and antimony in copper electrolyte | |
| CN102269733A (en) | Detection method for content of trace selenium in low alloy steel | |
| CN110865069A (en) | Method for measuring titanium content in ferrochrome alloy by using inductively coupled plasma emission spectrometer | |
| CN103674932A (en) | Method for determining content of Cu, Mn and Sn in Cu-Mn-Sn alloyed powder through ICP (inductively coupled plasma) | |
| CN102393371B (en) | Sample processing method for detecting boron in industrial silicon with graphite furnace atomic absorption spectrometry | |
| CN108871927A (en) | A kind of method of metals content impurity in measurement thorium anhydride | |
| CN111443079A (en) | Method for simultaneously detecting contents of trace As, Pb, Cd, Zn, Cr, Co and V elements in ferric trichloride | |
| CN109738419B (en) | Method for measuring boron content in aluminum-based boron carbide material | |
| CN113504191A (en) | Method for measuring content of trace iron and aluminum in nickel-based solution | |
| CN109557079A (en) | The ICP-OES measuring method of constituent content in sintering dust separation ash | |
| CN101609040A (en) | Method for continuously measuring iron, copper and manganese in sulfuric acid by flame atomic absorption method | |
| CN101639443A (en) | Method for rapidly and accurately determining sulphur element content in fluorite | |
| CN111257097A (en) | Vanadium carbide sample to be tested manufacturing method and impurity content analysis method thereof | |
| CN101710075A (en) | Method for measuring microelement in sodium aluminate solution | |
| CN108414505A (en) | A kind of method of copper, lead, Zn-ef ficiency content in measurement silver alloy | |
| CN110412116B (en) | Method for testing content of sulfur element and application thereof | |
| CN111965123A (en) | Method for measuring trace heavy metal lead by inhibition kinetics photometry | |
| CN115508340B (en) | Method for detecting impurities in sodium tungstate by using inductively coupled plasma emission spectrometer | |
| CN110749559A (en) | Rapid detection method for low-content silicon in aluminum and aluminum alloy | |
| CN116297408A (en) | HG-ICP-AES determination method for lead, arsenic, tin, antimony and bismuth in ferromolybdenum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |