CN110361441A - The detection method of micro impurity element in a kind of tungsten carbide powder - Google Patents
The detection method of micro impurity element in a kind of tungsten carbide powder Download PDFInfo
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Abstract
The invention discloses a kind of detection methods of micro impurity element in tungsten carbide powder, specifically 0.0001% is respectively less than using 18 kinds of impurity elements, the Determination Limits of impurity element such as inductively coupled plasma mass spectrometry Rapid Simultaneous Determination magnesium, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuths.Tungsten carbide sample is oxidized to tungstic acid by this method in high temperature furnace, sample is cleared up with ammonium hydroxide again, efficiently solve the problems, such as largely insoluble free carbon interference when tungsten carbide Wet Decomposition, and matrix depression effect is eliminated using tungsten basal body matching working curve, it is measured with icp ms.This method is easy to operate, and detection elements are more, and detection speed is fast, and Determination Limit is low, reaches trace rank, and with high accuracy, is suitable for the batch production analysis of high-quality or high-purity tungsten carbide.
Description
Technical field
The present invention relates to micro in high-purity material trace impurity analysis technical field more particularly to a kind of tungsten carbide powder
The detection method of impurity element, and in particular to using icp ms measurement tungsten carbide powder in magnesium, aluminium, calcium,
18 kinds of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth impurity contents.
Background technique
Primary raw material of the tungsten carbide powder as CEMENTED CARBIDE PRODUCTION, wherein the content of impurity element is hart metal product matter
Measure the important indicator of control.Currently, there is the examination criteria of micro impurity element content in tungsten carbide powder: professional standard YS/T559-
2009 and standard GB/T/T4324.1~30-2012.
" the emission spectrographic analysis method of YS/T 559-2009 tungsten " is direct-current arc atomic emission spectrometry.This method needs
Spectrum is taken the photograph, blackness is measured, analytical procedure is cumbersome, and relies on solid etalon sample and establish working curve, and analysis lower limit can not expire
The testing requirements of the high-purity tungsten carbide of foot；
" GB/T4324.1~30-2012 tungsten chemical analysis method " series standard is single element measuring method, analysis effect
Rate is low, is not able to satisfy the requirement of rapid multi-element analysis.
The report of impurities analysis is few in tungsten carbide powder, and wherein most is that high-content is mixed in analysis doping tungsten carbide
Miscellaneous element.There is the analysis document of micro impurity element in tungsten carbide powder:
Disclosed in CN103257136A Chinese patent " a method of calcium, cobalt, chromium, ferro element in measurement tungsten carbide " it is point
4 kinds of elements in WC-Co10-Cr4 tungsten carbide high temperature alloy are analysed, wherein cobalt, chromium content are greater than 1%, are not belonging to trace element analysis；
" a kind of detection method for measuring impurity element in tungsten carbide ", this method disclosed in CN105823772A Chinese patent
Be using inductively coupled plasma atomic emission spectrometry measurement tungsten carbide and cast tungsten carbide in cobalt, nickel, iron, titanium, aluminium,
Manganese, magnesium, vanadium, chromium, copper, molybdenum amount, this method cannot clear up the trip in tungsten carbide using strong acid dissolutions samples such as hydrofluoric acid, nitric acid
Accurate Determining is unable to from carbon, and to the element less than 0.0001%；
" analyzing detecting method of cobalt, nickel, iron, titanium and chromium in tungsten carbide " is to adopt disclosed in CN103529015A Chinese patent
Tungsten carbide sample is dissolved with sulfuric acid-ammonium sulfate, and uses citric acid complex tungsten, reagent blank is high, the measurement of unsuitable trace impurity.
" standard disclosed in 266-269 pages of the phase of " Yantai Normal College's journal (natural science edition) " 2001 volume 17 the 04th
Micro Fe in aas determination tungsten carbide, Mg, Ca, the content of K and Na is added ", which uses atomic absorption light
Spectrometry, single element measurement, and constituent content is measured 0.01% or more；
" measurement of trace arsenic in tungsten carbide and its compound " disclosed in 40-41 pages of the phase of " modern instrument " 1999 the 05th is
Using hydrogenation separation and culture Spectrophotometric Determination of Trace arsenic, measured for single element.
Inductively coupled plasma mass spectrometry (ICP-MS) is the advanced technology of trace element analysis research and application, is had
High sensitivity, detection limit be low, spectral line interference is less and the advantages that multielement simultaneous determination, is widely used in trace member in high-purity material
The measurement of element, but relevant report yet there are no for the analysis of micro impurity element in high-purity tungsten carbide.Using inductive coupling etc. from
There is the report of impurity element in daughter mass spectrometric determination high purity tungsten:
" inductively coupled plasma mass spectrometry measurement is high-purity disclosed in 403-406 pages of the phase of " analytical chemistry " 2009 the 03rd
4%H is used in phosphorus and other microelements in ammonium paratungstate "2O2Ammonium paratungstate is cleared up, tungsten carbide cannot be cleared up；
" the ICP-MS measurement of impurity in pure tungsten product disclosed in 43-46 pages of the phase of " Chinese Tungsten Industry " 2009 volume 24 the 01st
Technique study ", using H2O2Tungsten product is cleared up, tungsten carbide cannot be completely dissolved to limpid；
The 4th phase of volume 32 " mass spectrum journal " in July, 2011, " inductively coupled plasma mass spectrometry measured in high purity tungsten 15 kinds
Trace impurity " dissolves tungsten powder, tungsten rod sample with hydrofluoric acid-nitric acid, cannot clear up tungsten carbide powder completely, and need to be added
Internal standard compensates matrix effect, is readily incorporated micro impurity element；
" ion chromatography-film removes molten-ICP- disclosed in " assay office " 104-106 pages of the phase of volume 28 the 1st of in January, 2009
H is used in trace metal impurity in MS method measurement high purity tungsten "2O2After dissolving metal tungsten powder, exchanged by the cation of ion chromatography
After separating tungsten basal body, ICP-MS is measured after film goes dissolving device to be atomized.Analytical equipment is complicated, and is not suitable for tungsten carbide sample；
" inductively coupled plasma mass spectrometry is surveyed disclosed in 309-314 pages of the phase of " hard alloy " 2014 volume 31 the 05th
Determine 26 kinds of trace impurities in high purity tungsten " using H2O2High purity tungsten sample is dissolved, tungsten carbide cannot be completely dissolved.
Summary of the invention
The object of the present invention is to provide a kind of molten sample is high-efficient, analysis lower limit is low, and ten is several in tungsten carbide easy to operate
The rapid detection method of micro impurity element.
The present invention is by aoxidizing except carbon efficiently solves the resolution problem of tungsten carbide powder, using tungsten basal body matching criteria solution
It draws working curve and eliminates serious matrix depression effect, do not separate tungsten basal body, be also not required to add internal standard element, using inductive coupling
Plasma Mass Spectrometry measures 18 kinds of micro impurity elements in tungsten carbide simultaneously, and Determination Limit can reach 0.019 g/g~1.1 μ
μg/g.Method is accurate, reliably, easy quickly, it can be achieved that quick, the batch detection of high-purity tungsten carbide powder.
The detection method of micro impurity element, includes the following steps: in tungsten carbide powder of the invention
Step 1: tungsten carbide sample is aoxidized, the sample after being aoxidized；
Step 2: obtaining digestion solution with the sample after ammonium hydroxide resolution oxidation；
Step 3: obtaining the content of the micro impurity element in digestion solution.
In some embodiments of the invention, it in the step 3, including is measured with icp ms
In digestion solution the step of the content of impurity element.
In some embodiments of the invention, in the step 1, the temperature aoxidized to tungsten carbide sample is 600~
800 DEG C, the time of oxidation is 5~20min.
In some embodiments of the invention, in the step 2, the amount of the amount of the ammonium hydroxide and the tungsten carbide sample
Volume mass ratio be 10~20mL:1g.
In some embodiments of the invention, in the step 2, further include in the sample after ammonium hydroxide resolution oxidation
Low temperature heating step.
In some embodiments of the invention, in the low temperature heating step in the step 2, low-temperature heat temperature is 100
~150 DEG C.
In some embodiments of the invention, the quality of tungsten carbide sample and the obtained volume of digestion solution in step 1
Between quality volume thinner ratio be 1g:1000mL~10000mL.
In some embodiments of the invention, the micro impurity element be selected from magnesium, aluminium, calcium, titanium, vanadium, chromium, manganese, iron,
One of 18 kinds of cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead and bismuth micro impurity elements are a variety of, and preferably 18 kinds.
In some embodiments of the invention, the step 3 includes:
Step 3 (1), series standard solution are prepared: being cleared up high-purity tungsten basal body, be separately added into different amounts of impurity element
Solution forms impurity element series of concentrations；Preferably, high-purity tungsten basal body is ammonium paratungstate or tungsten powder；Preferably, the ammonia
Water further includes low temperature heating step during clearing up high-purity tungsten basal body；Preferably, in the low temperature heating step, heating temperature is
100~150 DEG C；
Step 3 (2) is marked using the digestion solution and series of icp ms measurement tungsten carbide sample
Quasi- sample；Preferably, the measurement running parameter of solution optimization icp ms is tuned before measurement using mixing,
Make oxide ion interference less than 1.5%, double-charge ion is interfered less than 3%；
Step 3 (3) establishes working curve and calculates sample impurity content.
In some embodiments of the invention, the mixing tuning solution includes lithium, yttrium, cerium, thallium, cobalt, and medium is nitric acid；
Preferably, it is described mixing tuning solution in lithium, yttrium, cerium, thallium, cobalt mass-volume concentration be 5-15ng/mL, preferably 10ng/
ML, medium 1.5-2.5%, the preferably nitric acid of 2% volume fraction.
In some embodiments of the invention, the solution containing micro impurity element includes the mixed liquor of calcic, molybdenum, lead
1 and containing aluminium, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium, vanadium mixed liquor 2；Preferably, the mixed liquor 1
Middle calcium, molybdenum, lead mass-volume concentration be 0.5-1.5 μ g/mL, preferably 1 μ g/mL, medium 2.0-3.0%, preferably 2.5%
The nitric acid of volume fraction, the matter of aluminium, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium, vanadium in the mixed liquor 2
Measuring volumetric concentration is 0.5-1.5 μ g/mL, preferably 1 μ g/mL, medium 2.0-3.0%, the preferably nitre of 2.5% volume fraction
Acid；It is further preferred that the mixed liquor 1 is diluted by mixed standard solution A, calcium in the mixed standard solution A, molybdenum,
The mass-volume concentration of lead is 40-60 μ g/mL, preferably 50 μ g/mL, medium 2.0-3.0%, preferably 2.5% volume fraction
Nitric acid, the mixed liquor 2 dilutes by mixed standard solution B, aluminium in the mixed standard solution B, arsenic, bismuth, cadmium, cobalt,
Chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium, vanadium mass-volume concentration be 80-120 μ g/mL, preferably 100 μ g/mL, medium
For 2.0-3.0mol/L, preferably 2.5mol/L hydrochloric acid, trace nitric acid, hydrofluoric acid (；Still more preferably, the hybrid standard
Solution A and mixed standard solution B are formulated by single element normal storage solution, the single element normal storage solution difference
It being formulated with primary standard substance, the mass-volume concentration of element is 800-1200 μ g/mL in the single element normal storage solution,
It is preferred that 1000 μ g/mL.
In some embodiments of the invention, the operating condition of the icp ms are as follows: transmitting function
900~1300W of rate, sample introduction 8.4~16.8mm of depth, 0.75~0.93L/min of carrier gas flux, compensation current amount 0.21~
0.68L/min, 0.3~1sec of the time of integration, 3 peak measurements, pendulous frequency 3 times.
In some embodiments of the invention, ammonium hydroxide (ρ 0.90g/mL), MOS grades or high-purity；Analysis is ultrapure water with water
(>=18.3M Ω cm) or secondary distilled water.
In some embodiments of the invention, 0.1~0.5g tungsten carbide sample is weighed, is placed in 80~150mL beaker, in
It is aoxidized in Muffle furnace complete.It is cooling, 10mL water, 1~10mL ammonium hydroxide, low-temperature heat dissolved clarification is added.Remove slightly cold i.e. immigration capacity
It is with water that solution is dilute to 20mL in bottle, it mixes.1000 μ L test solutions are pipetted in volumetric flask, dilute to 50mL with water, mixing is to be measured.
Reagent blank is done in company with sample.High-purity tungsten basal body (ω >=99.999%) of tungsten amount suitable with tungsten carbide sample is weighed in beaker
In, 25mL water, 1~10mL ammonium hydroxide, low-temperature heat dissolved clarification is added, and steam to about 15mL.It removes in slightly cold i.e. immigration volumetric flask, uses
Water is dilute to 20mL by solution, mixes.It pipettes the high-purity tungsten basal body test solution of 1mL to be respectively placed in 5 50mL volumetric flasks, is separately added into 0
~300 μ L mixed liquors 1 and mixed liquor 2, are diluted with water to scale, mix.The preparation method of mixed standard solution A and B are difference
It is mixed with single mark storage solutions grouping dilution of each element；Nitric acid used, hydrofluoric acid, hydrochloric acid are MOS grades or high-purity examination
Agent.Oxidizing temperature is 600~800 DEG C；Oxidization time is 5~20min；Low-temperature heat temperature is 100~150 DEG C.
The Determination Limit (10 σ) of 18 kinds of impurity elements is in icp ms measurement tungsten carbide
0.019 μ of μ g/g~1.1 g/g.
Beneficial effects of the present invention:
The present invention is few for existing detection method analytical element, lower limit for height is analyzed, in 0.0010% following analysis low precision
The problem of, propose a kind of method of 18 kinds of micro impurity elements analysis in tungsten carbide.And the present invention solves tungsten carbide
When Wet Decomposition largely insoluble free carbon interference measurement the problem of, solve the problems, such as tungsten carbide sample difficulty resolution, digestive reagent
Type and dosage are less, and eliminate mass spectrum interference by the best isotope of optimum choice element to be measured, are matched using tungsten basal body
Working curve eliminates tungsten basal body depression effect, and detection elements are more, and detection speed is fast, and Determination Limit is low, reaches trace rank, and
It is with high accuracy, it is suitable for the batch production analysis of high-quality or high-purity tungsten carbide.This method is easy to operate, and measurement is quick,
As a result accurate and reliable, the needs of research and production can be met.
The invention proposes a kind of method that ten several micro impurity elements quickly detect in tungsten carbide powder, technical advantage exists
In:
A. it solves the problems, such as free carbon interference sample introduction measurement in tungsten carbide powder, free carbon, oxygen will be removed after sample oxidation
It is fast to change speed, it is easy to operate.
B. digestive reagent dosage is few, without using the strong corrosives reagents such as nitric acid, hydrofluoric acid, hydrogen peroxide, digestion procedure letter
It is single, it is economic and environment-friendly.
C. sample does not need to be separated tungsten basal body, without Internal standard correction methods, eliminates matrix with high purity tungsten Matrix Match standard solution
Effect, and optimize instrument operating condition and reduce mass spectrum interference, it is with high accuracy.
D. 18 kinds of impurity contents in tungsten carbide can be measured simultaneously, and analytical element is more, and analysis speed is fast, analyzes lower limit
It is low, reach ng/g rank.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Embodiment 1
Measure magnesium in 02 type superfine tungsten carbide sample, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium,
This 18 kinds of impurity element amounts of tin, antimony, lead, bismuth.
(1) preparation of reagent and standard solution
Ammonium hydroxide (ρ 0.90g/mL), MOS grades；
Analysis is ultrapure water (>=18.3M Ω cm) with water；
18 kinds of impurity element single element normal storage solution: 1000 μ g/mL are formulated with primary standard substance respectively.
Mixed standard solution A: calcic, molybdenum, lead, mass-volume concentration are 50 μ g/mL, and medium is 2.5% nitric acid (volume
Score).
Mixed standard solution 1: calcic, molybdenum, 1 μ g/mL of lead, medium are 2.5% nitric acid, diluted by mixed standard solution A and
At.
Mixed standard solution B: contain aluminium, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium, vanadium, quality volume
Concentration is 100 μ g/mL, and medium is that 2.5mol/L hydrochloric acid, trace nitric acid, hydrofluoric acid, wherein trace nitric acid and hydrofluoric acid are medium,
It is brought into when single target medium.
Mixed standard solution 2: containing aluminium, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium, 1 μ g/mL of vanadium, is situated between
Matter is 2.5% nitric acid (volume fraction), is diluted by mixed standard solution B.
Lithium, yttrium, cerium, thallium, cobalt mixing tuning liquid: 10ng/mL, medium are 2% nitric acid (volume fraction).
(2) resolution of sample
0.25g tungsten carbide sample is weighed, is placed in 100mL beaker, 750 DEG C of oxidation 10min in Muffle furnace.It is cooling,
10mL water, 6mL ammonium hydroxide, in heating dissolved clarification on 120 DEG C of electric hot plates is added.It removes, is moved immediately after cooling 2~5min
Enter in volumetric flask, it is with water that solution is dilute to 20mL, it mixes.1000 μ L test solutions are pipetted in volumetric flask, it is dilute extremely with water
50mL is mixed, to be measured.Reagent blank is done in company with sample.
(3) working curve series standard solution is prepared
The high-purity ammonium paratungstate matrix (ω >=99.999%) of tungsten amount suitable with tungsten carbide sample is weighed in beaker, is added
25mL water, 6mL ammonium hydroxide, low-temperature heat dissolved clarification, and steam to about 15mL.It removes in slightly cold i.e. immigration volumetric flask, it is with water that solution is dilute
To 20mL, mix.It pipettes the high-purity tungsten basal body test solution of 1mL to be respectively placed in 5 50mL volumetric flasks, is separately added into 0~300 μ L mixing
Standard solution 1 and mixed standard solution 2, are diluted with water to scale, mix.
(4) it measures
Optimize Instrument working parameter using mixing tuning solution, makes oxide ion interference less than 1.5%, double-charge ion
Interference is less than 3%.Select the isotope of impurity element are as follows:24Mg、27Al、40Ca、48Ti、51V、52Cr、55Mn、56Fe、59Co、60Ni
、63Cu、75As、95Mo、114Cd、120Sn、121Sb、208Pb、209Bi。
Test solution, reagent blank and series standard solution series are measured on icp ms simultaneously,
Draw working curve, calculated result.
The present embodiment tungsten carbide sample is 30min from the resolution complete time is oxidized to.Ten in the present embodiment tungsten carbide sample
The testing result of eight kinds of impurity elements is shown in Table 1:
The testing result of 1 embodiment 1 of table
Embodiment 2
Measure magnesium in 06 type tungsten carbide powder sample, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin,
18 kinds of impurity element amounts such as antimony, lead, bismuth, and carry out precision measurement.
(1) preparation of reagent and standard solution
Ammonium hydroxide (ρ 0.90g/mL), it is high-purity；
Water secondary distilled water (>=18.3M Ω cm) is used in analysis；
The same below embodiment 1.
(2) resolution of sample
0.5g tungsten carbide sample is weighed, is placed in 100mL beaker, 700 DEG C of oxidation 12min in Muffle furnace.It is cooling, it is added
10mL water, 10mL ammonium hydroxide, in heating dissolved clarification on 150 DEG C of electric hot plates.It removes in slightly cold i.e. immigration volumetric flask, it is with water that solution is dilute extremely
20mL is mixed.1000 μ L test solutions are pipetted in volumetric flask, dilute to 50mL with water, mixing is to be measured.Reagent blank is done in company with sample.
(3) working curve series standard solution is prepared
With embodiment 1.
(4) it measures
With embodiment 1.
The precision of sample is tested
Replication 11 times on icp ms to test solution carry out method precision test, calculate
Measure average value and relative standard deviation (RSD).Measurement result is shown in Table 2.
The replication result of 2 embodiment 2 of table
Embodiment 3
Measure magnesium in 02 type tungsten carbide powder sample, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin,
18 kinds of impurity element amounts such as antimony, lead, bismuth, and be compared with the result of direct-current arc atomic emission spectrometry (AES) measurement.
(1) preparation of reagent and standard solution
With embodiment 1.
(2) resolution of sample
0.1g tungsten carbide sample is weighed, is placed in crucible, 800 DEG C of oxidation 15min in Muffle furnace.It is cooling, 10mL is added
Water, 1mL ammonium hydroxide, in heating dissolved clarification on 100 DEG C of electric hot plates.Remove it is slightly cold move into volumetric flask, it is with water that solution is dilute to 20mL,
It mixes.10mL test solution is pipetted in volumetric flask, dilute to 100mL with water, mixing is to be measured.Reagent blank is done in company with sample.
(3) working curve series standard solution is prepared
With embodiment 1.
(4) it measures
With embodiment 1.
ICP-MS measurement result and the result of direct-current arc atomic emission spectrometry (Arc-AES) measurement compare, and are shown in Table 3.
3 embodiment 3 of table measures comparing result
As can be seen from the above table, the result that ICP-MS and Arc-AES measures 17 kinds of impurity elements is completely the same, Arc-AES is solid
There is no cadmium in body standard specimen working curve, cadmium cannot be measured, and Arc-AES is unable to accurate quantitative analysis to wherein 12 elements, it can only
It quotes and is less than result.
Embodiment 4
Measure simultaneously magnesium in 06 type tungsten carbide powder sample and tungstic acid standard specimen, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt,
18 kinds of impurity element amounts such as nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth carry out standard specimen control.
(1) preparation of reagent and standard solution
With embodiment 1.
(2) resolution of sample
With embodiment 2.
0.59g tungstic acid standard specimen is weighed, is placed in 100mL beaker, 8mL ammonium hydroxide is added, it is molten in being heated on 150 DEG C of electric hot plates
Clearly.It removes in slightly cold i.e. immigration volumetric flask, it is with water that solution is dilute to 20mL, it mixes.1000 μ L test solutions are pipetted in volumetric flask, are used
Water is dilute to 50mL, and mixing is to be measured.Reagent blank is done in company with sample.
(3) working curve series standard solution is prepared
With embodiment 1.
(4) it measures
With embodiment 1.
4 embodiment 4 of table and the measured value of standard specimen and standard value unit: (μ g/g)
Inductively coupled plasma mass spectrometry measures tungsten carbide sample and tungstic acid standard specimen simultaneously, the results are shown in Table 4, standard specimen
Measured value it is consistent with standard value height, it is seen that the accuracy of this method is high.
Embodiment 5
Measure high-purity tungsten basal body working curve blank solution 11 times, determine magnesium, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel,
The method Determination Limit of 18 kinds of impurity elements such as copper, arsenic, molybdenum, cadmium, tin, antimony, lead, bismuth.
(1) preparation of reagent and standard solution
With embodiment 1.
(2) working curve series standard solution is prepared
With embodiment 1.
(3) it measures
Optimize Instrument working parameter using mixing tuning solution, makes oxide ion interference less than 1.5%, double-charge ion
Interference is less than 3%.It is measured on icp ms, draws working curve.To the base in standard liquid series
Body blank solution calculates the mark of Determination of Impurity Elements value in blank solution METHOD FOR CONTINUOUS DETERMINATION 11 times under the conditions of selected experimental work
Quasi- deviations, 10 σ are method Determination Limit.It the results are shown in Table 5.
The method Determination Limit of 50 eight kinds of impurity elements of table
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. the detection method of micro impurity element, includes the following steps: in a kind of tungsten carbide powder
Step 1: tungsten carbide sample is aoxidized, the sample after being aoxidized；
Step 2: obtaining digestion solution with the sample after ammonium hydroxide resolution oxidation；
Step 3: obtaining the content of the impurity element in digestion solution；Preferably, in the step 3, including with inductive coupling
Plasma mass spectrograph measures the step of content of impurity element in digestion solution.
2. the method according to claim 1, wherein being aoxidized in the step 1 to tungsten carbide sample
Temperature is 600~800 DEG C, and the time of oxidation is 5~20min.
3. method according to claim 1 or 2, which is characterized in that in the step 2, the amount of the ammonium hydroxide and the carbon
The volume mass ratio for changing the amount of tungsten sample is 10~20mL:1g.
4. method according to claim 1 to 3, which is characterized in that in the step 2, after ammonium hydroxide resolution oxidation
It further include low temperature heating step in sample；Preferably, in the low temperature heating step, heating temperature is 100~150 DEG C.
5. method according to claim 1 to 4, which is characterized in that the quality of tungsten carbide sample described in step 1 with
Quality volume thinner ratio between the volume of step 2 digestion solution is 1g:1000mL~10000mL.
6. -5 any method according to claim 1, which is characterized in that the micro impurity element be selected from magnesium, aluminium, calcium,
One of this 18 kinds of micro impurity elements of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, molybdenum, cadmium, tin, antimony, lead and bismuth are more
Kind, preferably 18 kinds.
7. -6 any method according to claim 1, which is characterized in that the step 3 includes:
Step 3 (1), series standard solution are prepared: high-purity tungsten basal body cleared up, the solution of different amounts of impurity element is separately added into,
Form impurity element series of concentrations；Preferably, high-purity tungsten basal body is ammonium paratungstate or tungsten powder；Preferably, the ammonium hydroxide disappears
Solving high-purity tungsten basal body further includes in the process low temperature heating step；Preferably, in the low temperature heating step, heating temperature 100
~150 DEG C；
Step 3 (2), it is molten using the digestion solution and series standard of icp ms measurement tungsten carbide sample
Liquid；Preferably, make oxygen using the measurement running parameter of mixing tuning solution optimization icp ms before measurement
Less than 1.5%, double-charge ion is interfered less than 3% compound ion interference；
Step 3 (3) establishes working curve and calculates sample impurity content.
8. -7 any method according to claim 1, which is characterized in that the mixing tune solution include lithium, yttrium, cerium,
Thallium and cobalt, medium are nitric acid；Preferably, the mass-volume concentration for mixing lithium in tuning solution, yttrium, cerium, thallium and cobalt is
5-15ng/mL, preferably 10ng/mL, medium 1-1.5%, the preferably nitric acid of 2% volume fraction.
9. -8 any method according to claim 1, which is characterized in that the solution of the impure element include calcic,
The mixed liquor 1 of molybdenum and lead and mixed liquor 2 containing aluminium, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium；It is excellent
Selection of land, the mass-volume concentration of calcium, molybdenum and lead is 0.5-1.5 μ g/mL in the mixed liquor 1, and preferably 1 μ g/mL, medium is
2.0-3.0%, the preferably nitric acid of 2.5% volume fraction, aluminium in the mixed liquor 2, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese,
Nickel, antimony, tin, titanium and vanadium mass-volume concentration be 0.5-1.5 μ g/mL, preferably 1 μ g/mL, medium 2.0-3.0%, preferably
The nitric acid of 2.5% volume fraction；It is further preferred that the mixed liquor 1 is diluted by mixed standard solution A, the mixing
The mass-volume concentration of calcium, molybdenum and lead is 40-60 μ g/mL in standard solution A, preferably 50 μ g/mL, medium 2.0-3.0%,
It is preferred that the nitric acid of 2.5% volume fraction, the mixed liquor 2 is diluted by mixed standard solution B, the mixed standard solution B
Middle aluminium, arsenic, bismuth, cadmium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, antimony, tin, titanium and vanadium mass-volume concentration be 80-120 μ g/mL,
It is preferred that 100 μ g/mL, medium 2.0-3.0mol/L, preferably 2.5mol/L hydrochloric acid, trace nitric acid, hydrofluoric acid；Still more preferably
, the mixed standard solution A and mixed standard solution B are formulated by single element normal storage solution, the single element
Normal storage solution is formulated with primary standard substance respectively, the mass-volume concentration of element in the single element normal storage solution
For 800-1200 μ g/mL, preferably 1000 μ g/mL.
10. -9 any method according to claim 1, which is characterized in that the icp ms
Operating condition are as follows: 900~1300W of transmission power, sample introduction 8.4~16.8mm of depth, 0.75~0.93L/min of carrier gas flux are mended
Repay 0.21~0.68L/min of throughput, 0.3~1sec of the time of integration, 3 peak measurements, pendulous frequency 2-4 times, preferably 3 times.
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| 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 |
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