CN109900679A - A kind of method of silicon, manganese, molybdenum, iron, W content in measurement cobalt-base alloys - Google Patents
A kind of method of silicon, manganese, molybdenum, iron, W content in measurement cobalt-base alloys Download PDFInfo
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Abstract
The present invention provides a kind of method for measuring silicon, manganese, molybdenum, iron, W content in cobalt-base alloys, the following steps are included: 1) sample pre-treatments: weighing cobalt-base alloys sample, digestion agent is added, it is cooling after progress micro-wave digestion, after adding saturation boric acid solution progress confined reaction, transfer, constant volume obtain sample solution；2) preparation of standard solution: matrix solution is chosen, element to be measured is added, is made into standard solution；3) it measures: the standard solution of preparation, sample solution being subjected to inductively coupled plasma atomic emission spectrometer detection respectively, quantified using calibration curve method, the content of silicon, manganese, molybdenum, iron, wolfram element in sample solution is obtained.The method of silicon, manganese, molybdenum, iron, W content in a kind of measurement cobalt-base alloys provided by the invention, using preferred digestive reagent, the sealed microwave digestion method of optimum condition and ICP-AES measuring method, it is easy to operate, precision is good, accuracy is high, have it is preferable promote, application value.
Description
Technical field
The invention belongs to the chemical analysis technology field of metal material composition, be related to silicon in a kind of measurement cobalt-base alloys, manganese,
The method of molybdenum, iron, W content.
Background technique
Cobalt-base alloys, i.e., usually said cobalt chromium tungsten (molybdenum) alloy or Si Taili (Stellite) alloy (stellite
By American Elwood Hayness in inventing in 1907), it is a kind of abrasion of abilitys various types and corrodes and high-temperature oxydation
Hard alloy.Cobalt-base alloys is to make alloy as main component with cobalt, includes C, Mn, Si, Cr, Ni, Mo, Fe, W, Co etc.
Element, since cobalt is a kind of grand strategy resource, most countries lack cobalt in the world, so that the development of cobalt-base alloys is limited
System.General cobalt base superalloy lacks the hardening constituent of coherence, although medium temperature intensity is low (the only 50-75% of nickel-base alloy),
Intensity, good thermal fatigue resistance, corrosion and heat resistant and wear-corrosion resistance with higher when being higher than 980 DEG C, and have preferable weldering
Connecing property.Suitable for production aero-jet engine, industry gas turbine, the guide vane of Vessel personnel and nozzle guide vane and
Diesel nozzeles etc..Different according to ingredient in alloy, welding wire can be made in they, and powder is used for hard-face overlaying welding, thermal spraying, surfacing
Etc. techniques, forge piece and metallic sintered products can also be made.Therefore, it in order to effectively improve the performance of cobalt-base alloys, can also add
Some essential elements, it is seen then that it is necessary to effectively be detected to some of which important element, its content is controlled, in order to have
The quality of effect monitoring cobalt-base alloys.
Currently, method standard and not perfect, domestic none of special needle of standard to cobalt-base alloys elemental analysis
Elemental analysis to cobalt-base alloys, external also only ASTM E1473-09 are the chemical analysis methods about cobalt base superalloy
A standard, and be nearly all traditional chemical analysis method, for example, by using gravimetric method, titration, spectrophotometry and
Atomic absorption spectrography (AAS) etc..Such methods measurement element is single, and redundant and complicated operation, detection time is long, and consumption amount of reagent is more, dirty
Contaminate environment.Due to the scarcity of cobalt-base alloys standard, very big difficulty is caused to the Accurate Determining of the element of cobalt-base alloys.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide silicon in a kind of measurement cobalt-base alloys,
The method of manganese, molybdenum, iron, W content is measured for solving to lack in the prior art while analysis speed is fast, analysis result is accurate
In cobalt-base alloys the problem of the method for silicon, manganese, molybdenum, iron, tungsten.
In order to achieve the above objects and other related objects, the present invention provide silicon in a kind of measurement cobalt-base alloys, manganese, molybdenum, iron,
The method of W content, comprising the following steps:
1) sample pre-treatments: weighing cobalt-base alloys sample, and digestion agent is added, and carries out cooling after micro-wave digestion, adds full
After carrying out confined reaction with boric acid solution, transfer, constant volume obtain sample solution；
2) preparation of standard solution: matrix solution is chosen, element to be measured is added, is made into standard solution；
3) it measures: sample solution in the standard solution of step 2) preparation, step 1) being subjected to inductively coupled plasma respectively
Body Atomic Emission Spectrometer AES (ICP-AES) detection, quantify using calibration curve method, acquisition sample solution in silicon, manganese, molybdenum,
The content of iron, wolfram element.
Preferably, in step 1), the digestion agent is the mixed solution of hydrochloric acid, nitric acid, hydrofluoric acid.
It is highly preferred that the hydrochloric acid is the aqueous hydrochloric acid solution of 30-40% (percent by volume v/v%).It is further preferred that
The hydrochloric acid is the aqueous hydrochloric acid solution of 37% (percent by volume v/v%).It is highly preferred that the nitric acid is 60-65% (volume hundred
Point than v/v%) aqueous solution of nitric acid.It is further preferred that the nitric acid that the nitric acid is 65% (percent by volume v/v%) is water-soluble
Liquid.
It is highly preferred that the hydrofluoric acid is the hydrofluoric acid aqueous solution of 30-40% (percent by volume v/v%).It is further excellent
Selection of land, the hydrofluoric acid are the hydrofluoric acid aqueous solution of 40% (percent by volume v/v%).
It is highly preferred that in the mixed solution of the hydrochloric acid, nitric acid, hydrofluoric acid, the ratio between the hydrochloric acid, volume of nitric acid addition
For 3:1~10:1, it is≤2mL that volume, which is added, in the hydrofluoric acid, the hydrochloric acid, nitric acid, hydrofluoric acid total volume be 8~30mL.
It is further preferred that in the mixed solution of the hydrochloric acid, nitric acid, hydrofluoric acid, volume that the hydrochloric acid, nitric acid are added
The ratio between be 7:1, it is 1~2mL that volume, which is added, in the hydrofluoric acid, the hydrochloric acid, nitric acid, hydrofluoric acid total volume be 10~20mL.
Preferably, in step 1), volume (mL) that the quality (g) and digestion agent that the cobalt-base alloys sample is added are added it
Than for 1:100~1:350.It is highly preferred that the volume (mL) that quality (g) and digestion agent that the cobalt-base alloys sample is added are added
The ratio between be 1:180~1:200.
Preferably, in step 1), the micro-wave digestion clears up cobalt-base alloys sample using microwave dissolver
Method.The microwave dissolver is conventional use of micro-wave digestion equipment, and the microwave dissolver is furnished with micro-wave diminishing pot.It is described
Cobalt-base alloys sample is cleared up in micro-wave diminishing pot.
Preferably, in step 1), in the micro-wave digestion, the matching relationship of micro-wave diminishing pot number and power are as follows: 1-2 tank
Use power for 400W, 3-5 tank uses power for 800W, and 6-12 tank uses power for 1600W.The micro-wave digestion uses power
Minimization principle.
Preferably, in step 1), the temperature program of the micro-wave digestion are as follows: initial temperature is 20~30 DEG C, with 10~
The heating-up time of 15min rises to 100~120 DEG C, keeps 15~20min；140 are risen to again with the heating-up time of 10~15min~
150 DEG C, keep 15~30min.
It is highly preferred that the temperature program of the micro-wave digestion are as follows: initial temperature is 23-27 DEG C, with the heating-up time of 10min
120 DEG C are risen to, 15min is kept；150 DEG C are risen to the heating-up time of 15min again, keeps 30min.
Preferably, in step 1), the cooling temperature is room temperature.The room temperature is 20-25 DEG C.
Preferably, in step 1), the saturation boric acid solution is that the boric acid that mass percent concentration is 4-6wt% is water-soluble
Liquid.The saturation boric acid solution is that 4~7g boric acid is dissolved in 100mL hot water, and certain time, natural cooling, filtering is sufficiently stirred
The supernatant liquor of acquisition.The saturation boric acid solution can be such that boric acid reacts completely with excessive hydrofluoric acid.
Preferably, in step 1), hydrofluoric acid is added in the saturation boric acid solution and digestion agent the ratio between volume for 4:1~
10:1.It is highly preferred that the ratio between the volume that hydrofluoric acid is added in the saturation boric acid solution and digestion agent is 7:1.Preferably, step
1) in, the time of the confined reaction is 25-35min.It is highly preferred that the time of the confined reaction is 30min.
Preferably, in step 1), the transfer is that solution of the sample after reacted is transferred in dosing container.It is described fixed
Amount container is volumetric flask.When the transfer, digestion container is cleaned multiple times on a small quantity with water, the water is transferred to fixed together
It measures in container.
Preferably, in step 1), the constant volume is that constant volume is diluted with water in dosing container.Above-mentioned with water is ultrapure
Water.
Preferably, in step 2), the matrix solution be hydrochloric acid, nitric acid, chromium stock solution, cobalt stock solution mixed solution.
Due to containing a certain amount of chromium, cobalt background material in cobalt-base alloys sample, chromium, cobalt can generate interference to the measurement of element to be measured,
It needs to simulate the similar chromium of adding conditional in standard solution, cobalt carries out bottoming.
It is highly preferred that the hydrochloric acid is the aqueous hydrochloric acid solution of 30-40% (percent by volume v/v%).It is further preferred that
The hydrochloric acid is the aqueous hydrochloric acid solution of 37% (percent by volume v/v%).
It is highly preferred that the nitric acid is the aqueous solution of nitric acid of 60-65% (percent by volume v/v%).It is further preferred that
The nitric acid is the aqueous solution of nitric acid of 65% (percent by volume v/v%).
It is highly preferred that the chromium stock solution is the chromium-containing solution that concentration is 10mg/mL.The chromium stock solution is to weigh
After 2.829g first passes through 150 DEG C of baking 1h in advance, it is placed in the potassium bichromate (benchmark) being cooled to room temperature in drier, is placed in a beaker,
It is dissolved with water, moves into 100mL volumetric flask, be diluted with water to scale, shake up to obtain.
It is highly preferred that the cobalt stock solution is the aqueous solution containing cobalt that concentration is 50mg/mL.The cobalt stock solution is to weigh 5g
Pure cobalt is placed in a beaker, and uses 40mLHNO3Aqueous solution (1 part of HNO3+ 3 parts of water) dissolution, it is cooling, it moves into 100mL volumetric flask, uses water
It is diluted to scale, shakes up to obtain.
It is highly preferred that in the matrix solution, the ratio between the hydrochloric acid, nitric acid, chromium stock solution, volume of cobalt stock solution addition
For 3~10:1:1~3:1~1.5.It is further preferred that in the matrix solution, the hydrochloric acid, nitric acid, chromium stock solution, cobalt storage
The ratio between the volume that standby liquid is added is 7:1:2.5:1.2.
Preferably, in step 2), the element to be measured is respectively silicon, manganese, molybdenum, iron, the wolfram element of a certain concentration content
Single stock solution.
Preferably, in step 2), the standard solution is a series of the siliceous of various concentrations, manganese, molybdenum, iron, wolfram element
Matrix solution.
Preferably, in step 2), in the standard solution, concentration≤5.00wt% of the element silicon.Further preferably
Ground, in the standard solution, the concentration of the element silicon is≤3.00wt%.
Preferably, in step 2), in the standard solution, the concentration of the manganese element is≤4.00wt%.It is further excellent
Selection of land, in the standard solution, the concentration of the manganese element is≤2.00wt%.
Preferably, in step 2), in the standard solution, concentration≤8.00wt% of the molybdenum element.Further preferably
Ground, in the standard solution, concentration≤7.00wt% of the molybdenum element.
Preferably, in step 2), in the standard solution, concentration≤5.00wt% of the ferro element.Further preferably
Ground, in the standard solution, concentration≤4.00wt% of the ferro element.
Preferably, in step 2), in the standard solution, concentration≤8.00wt% of the wolfram element.Further preferably
Ground, in the standard solution, concentration≤6.00wt% of the wolfram element.Preferably, in step 3), described inductive coupling etc. from
The instrument testing conditions of daughter atom emission spectrometer (ICP-AES) are as follows:
RF transmission power: 950,1150,1350,1500 or 1600KW；Cooling air (plasma (orifice) gas): argon gas；Cooling air (etc.
Ion-gas) flow: 10-20L/min；Atomization gas (carrier gas): argon gas；Atomization gas (carrier gas) flow: 0.5-1.5L/min；Auxiliary
Gas: argon gas；Secondary air amount: 0.1-2L/min；Sample lifting capacity: 1-5mL/min；Observed pattern: horizontal or vertical；Observation is high
Degree: 5-15mm；Washing time: 30-50s；The shortwave time of integration: 15-25s；The long wave time of integration: 3-10s.
It is highly preferred that the instrument testing conditions of the ICP-AES are as follows:
RF transmission power: 1150KW；Cooling air (plasma (orifice) gas): argon gas；Cooling air (plasma (orifice) gas) flow: 12L/min；
Atomization gas (carrier gas): argon gas；Atomization gas (carrier gas) flow: 0.7L/min；Assist gas: argon gas；Secondary air amount: 0.5L/min；
Sample lifting capacity: 2mL/min；Observed pattern: vertical；Observed altitude: 12mm；Washing time: 40s；The shortwave time of integration: 20s；
The long wave time of integration: 5s.
The inductively coupled plasma atomic emission spectrometer (ICP-AES) is equipped with HF acid resistant device.It is described
HF acid resistant device is the atomizer, spray chamber and corundum material of the polytetrafluoroethylene (PTFE) material with hydrofluoric acid resistant
Core pipe can strictly prevent hydrofluoric acid from polluting and corroding ICP-AES.
Preferably, in step 3), the analytical line wave of the inductively coupled plasma atomic emission spectrometer (ICP-AES)
It is long are as follows: silicon (Si): 251.611,288.158nm；Manganese (Mn): 257.610,259.373nm；Molybdenum (Mo): 204.598,
202.032nm；Iron (Fe): 259.940,238.204nm, tungsten (W): 207.911,209.475nm.
It is highly preferred that being tested the analysis of line wavelength of element in the ICP-AES are as follows: silicon (Si): 251.611nm；Manganese (Mn):
257.610nm；Molybdenum (Mo): 204.598nm；Iron (Fe): 259.940nm, tungsten (W): W content >=1wt%, 207.911nm, tungsten
Content < 1wt%, 209.475nm.
Preferably, in step 3), the calibration curve method the following steps are included:
A, a series of standard solution of the various concentrations obtained in step 2) is subjected to ICP-AES detection, obtained respectively every
The analytical line intensity of element kind to be measured than with the linear relationship of the mass concentration of corresponding element to be measured, it is molten to draw corresponding standard
Liquid working curve calculates separately to obtain the regression equation of the standard working curve of 5 kinds of elements to be measured.
More preferably, in the standard curve, using the analytical line intensity ratio of every kind of element to be measured as ordinate (Y-axis), phase
The mass concentration for answering element to be measured is abscissa (X-axis).
B, sample solution in step 1) is subjected to ICP-AES detection, by every kind of element to be measured in the sample solution of acquisition
Analytical line intensity ratio substitutes into the regression equation of the standard working curve of corresponding element to be measured in step A, and according in standard solution
The known quality concentration of corresponding element to be measured, is calculated the mass concentration of corresponding element to be measured in sample solution.
As described above, a kind of method for measuring silicon, manganese, molybdenum, iron, W content in cobalt-base alloys provided by the invention, uses
Preferred digestive reagent, the sealed microwave digestion method of optimum condition and ICP-AES measuring method, breach cobalt-base alloys indissoluble and Si
The technological difficulties that element is volatile, wolframic acid is easily precipitated, molybdenum content measured value is unstable solve ICP-AES measurement cobalt-base alloys
Many problems that multielement content is faced, such as the screening of element analysis spectrum line to be measured, the elimination of matrix effect, interference element
Correction and removing method, optimization, the background correction of instrument analysis parameter etc., so that accurately measurement cobalt-base alloys multielement contains
Amount.Measuring method in the present invention selects microwave digestion technology as sample pretreatment technology, there is sample to decompose completely, fastly
Speed, the advantage that reagent dosage is few, low latitude is white etc., can guarantee that cobalt base hard alloy is completely dissolved, avoid precipitation and the silicon of wolframic acid
Volatilization.Measuring method in the present invention is selected inductively coupled plasma emission spectrography (ICP-AES), is had linear
Range is wide, the features such as being known as preferable sensitivity to high temperature alloy member, can simultaneously or sequentially measuring multiple element, to measurement cobalt-based
Si, Mo, Mn, Fe, elements such as w have biggish superiority in alloy.Measuring method in the present invention, easy to operate, precision
Good, accuracy height, has preferable popularization, application value.
Specific embodiment
The present invention is further explained combined with specific embodiments below, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Reagent used in the present invention and instrument are as follows:
1, reagent
Cobalt-base alloys sample (Lincoln's welding material (Beijing) Co., Ltd)；Hydrochloric acid, nitric acid, hydrofluoric acid, boric acid (analysis
It is pure, Shanghai Ling Feng chemical reagents corporation)；Silicon stock solution, manganese stock solution, molybdenum stock solution, Blood lipids liquid, (concentration is equal for tungsten stock solution
For 1mg/mL, national steel material test center)；Water (water purification machine self-control)；Potassium bichromate (benchmark, Shanghai Ling Feng chemical reagent
Company)；Pure cobalt (purity >=99.99%, national steel material test center).
2, instrument
ICAP-6500 type inductively coupled plasma atomic emission spectrometer (it is equipped with frequency 27.12MHz RF generator,
Power & light company, the U.S.)；HF acid resistant device (the Radial HF Kit that number is 8,423 1,200 51121, U.S.'s thermoelectricity
Company)；5 type microwave dissolver of MARS (U.S. CE M company).
Embodiment 1
1, sample pre-treatments
Cobalt-base alloys sample is weighed, digestion agent is added, carries out cooling after micro-wave digestion, saturation boric acid solution is added and carries out
After confined reaction, transfer, constant volume obtain sample solution.Wherein, digestion agent is the mixed solution of hydrochloric acid, nitric acid, hydrofluoric acid.Salt
Acid, nitric acid, hydrofluoric acid mixed solution in, the ratio between volume that hydrochloric acid, nitric acid are added is 3:1~10:1, and volume is added in hydrofluoric acid
For≤2mL, hydrochloric acid, nitric acid, hydrofluoric acid total volume be 8~30mL.The quality (g) that cobalt-base alloys sample is added adds with digestion agent
The ratio between volume (mL) entered is 1:100~1:350.
In addition, micro-wave digestion is the method cleared up using microwave dissolver to cobalt-base alloys sample, microwave dissolver
Equipped with micro-wave diminishing pot, cobalt-base alloys sample is cleared up in micro-wave diminishing pot.In micro-wave digestion, micro-wave diminishing pot number with
The matching relationship of power are as follows: 1-2 tank uses power for 400W, and 3-5 tank uses power for 800W, 6-12 tank use power for
1600W.The temperature program of micro-wave digestion are as follows: initial temperature is 20~30 DEG C, 100 are risen to the heating-up time of 10~15min~
120 DEG C, keep 15~20min；140~150 DEG C are risen to the heating-up time of 10~15min again, keeps 15~30min.It is cooling
Temperature is room temperature.
Saturation boric acid solution is the boric acid aqueous solution that mass percent concentration is 4-6wt%.The saturation boric acid solution with
The ratio between volume that hydrofluoric acid is added in digestion agent is 4:1~10:1.The time of confined reaction is 25-35min.Transfer is by sample
Solution after reacted is transferred in dosing container, digestion container is cleaned multiple times on a small quantity with water, the water turns together
It moves in dosing container.
2, the preparation of standard solution
Matrix solution is chosen, a series of element to be measured of various concentrations is added, a series of standard for being made into various concentrations is molten
Liquid.Wherein, matrix solution be hydrochloric acid, nitric acid, chromium stock solution, cobalt stock solution mixed solution.Chromium stock solution is that concentration is 10mg/
The chromium-containing solution of mL.Cobalt stock solution is the aqueous solution containing cobalt that concentration is 50mg/mL.In matrix solution, the hydrochloric acid, nitric acid,
The ratio between the volume that chromium stock solution, cobalt stock solution are added is 3~10:1:1~3:1~1.5.Standard solution is a series of various concentrations
Siliceous, manganese, molybdenum, iron, wolfram element matrix solution, concentration≤5.00wt% of element silicon, the concentration of manganese element≤
4.00wt%, concentration≤8.00wt% of molybdenum element, concentration≤5.00wt% of ferro element, the concentration of wolfram element is≤
8.00wt%.
3, the measurement of sample
Sample solution in step 2 Plays solution and step 1 is subjected to inductively coupled plasma body atomic emissions light respectively
Spectrometer (ICP-AES) detection, quantify using calibration curve method, and silicon, manganese, molybdenum, iron, wolfram element contain in acquisition sample solution
Amount.
Specifically, a series of standard solution of the various concentrations obtained in above-mentioned steps 2 is first subjected to ICP-AES inspection
Survey, obtain respectively the analytical line intensity of every kind of element to be measured than with the linear relationship of the mass concentration of corresponding element to be measured, with
The analytical line intensity ratio of every kind of element to be measured is ordinate (Y-axis), and the mass concentration of corresponding element to be measured is abscissa (X
Axis), it calculates separately to obtain the regression equation of the standard working curve of 5 kinds of elements to be measured.
Then, ICP-AES detection then by sample solution in step 1 is carried out, by every kind of member to be measured in the sample solution of acquisition
The analytical line intensity ratio of element substitutes into the regression equation of the standard working curve of corresponding element to be measured, and according to phase in standard solution
The mass concentration of corresponding element to be measured in sample solution is calculated in the known quality concentration for answering element to be measured.For ICP-
Instrument working parameter, according to the content and property of each element, the element to be measured recommended from instrument software spectral line library is arranged in AES
In spectral line, several sensitive lines is selected to carry out spectral line screening, measures each element content.
The instrument testing conditions of ICP-AES are as follows: RF transmission power: 950,1150,1350,1500 or 1600KW；Cooling air
(plasma (orifice) gas): argon gas；Cooling air (plasma (orifice) gas) flow: 10-20L/min；Atomization gas (carrier gas): argon gas；Atomization gas (carries
Gas) flow: 0.5-1.5L/min；Assist gas: argon gas；Secondary air amount: 0.1-2L/min；Sample lifting capacity: 1-5mL/min；
Observed pattern: horizontal or vertical；Observed altitude: 5-15mm；Washing time: 30-50s；The shortwave time of integration: 15-25s；Long wave
The time of integration: 3-10s.
The selection of 1 analysis spectral line of table
| Element | Wavelength/nm | It may interfere with element | Interference elimination method |
| Si | 251.611、288.158 | V, Co base | Background deduction (left and right) |
| Mn | 257.610、259.373 | W, Mo, Co base | Background deduction (left and right) |
| Mo | 204.598、202.032 | Co base | Background deduction (left and right) |
| Fe | 259.940、238.204 | Co base | Background deduction (left and right) |
| W | 207.911、209.475 | Co base | Background deduction (left and right) |
The analysis of line wavelength of element is tested in ICP-AES are as follows: silicon (Si): 251.611,288.158nm；Manganese (Mn):
257.610,259.373nm；Molybdenum (Mo): 204.598,202.032nm；Iron (Fe): 259.940,238.204nm, tungsten (W):
207.911,209.475nm.When the spectral line of each element is overlapped, cast aside spectral line be overlapped or part spectral line be overlapped it is sensitive
Line, selection intensity is big, and peak shape is good, high sensitivity, interferes the smallest spectral line as analytical line, and element analysis spectrum line sees the above table 1.
Embodiment 2
1, sample pre-treatments
0.1000g cobalt-base alloys sample is weighed, micro-wave diminishing pot is placed in, 14mLHCl, 2mLHNO is added3(about with 2mLHF
30 drops), in sample molten on microwave dissolver.In micro-wave digestion, the matching relationship of micro-wave diminishing pot number and power are as follows: 1-2 tank is adopted
It is 400W with power, 3-5 tank uses power for 800W, and 6-12 tank uses power for 1600W.The temperature program of micro-wave digestion are as follows:
Initial temperature is 23-27 DEG C, rises to 120 DEG C with the heating-up time of 10min, keeps 15min；Again with the heating-up time liter of 15min
To 150 DEG C, 30min is kept.
It is finished wait clear up, is cooled to 25 DEG C, take out micro-wave diminishing pot, being rapidly added 14mL mass percent concentration is 4-
The saturation boric acid solution of 6wt% is tightened micro-wave diminishing pot, is finished after 30min to confined reaction, and 100mL plastics volumetric flask is moved into
It is middle dilute to scale with water, it shakes up.
2, the preparation of standard solution
14mLHCl, 2mLHNO is added to the plastics volumetric flask that number is 0#-5# respectively3, 2.50mL 10mg/mL chromium deposit
Liquid and 1.20mL 50mg/mL cobalt stock solution, as matrix solution.Then to each volumetric flask be added the silicon of certain volume, manganese, nickel,
Molybdenum, iron and tungsten stock solution, preparing standard solution.In standard solution, concentration≤3.00wt% of element silicon, the concentration of manganese element
≤ 2.00wt%, concentration≤7.00wt% of molybdenum element, concentration≤4.00wt% of ferro element, the concentration of wolfram element is≤
6.00wt%.It is wherein blank solution in 0#, is the standard solution of each element content containing various concentration in 1#-5#, in 1-5#
0.50~2.00wt% of concentration of element silicon, 0.20~2.00wt% of concentration of manganese element, the concentration 1.00 of molybdenum element~
7.00wt%, 0.50~4.00wt% of concentration of ferro element, the concentration of wolfram element are 1.00~6.00wt%.Since tungsten, molybdenum are easy
Hydrolysis, the standard solution preferably same day prepare.
3, the measurement of sample
Sample solution in step 1 and step 2 Plays solution are subjected to inductively coupled plasma body atomic emissions light respectively
Spectrometer (ICP-AES) detection, quantify using calibration curve method, and silicon, manganese, molybdenum, iron, wolfram element contain in acquisition sample solution
Amount.
Specifically, a series of standard solution of the various concentrations obtained in above-mentioned steps 2 is first subjected to ICP-AES inspection
Survey, obtain respectively the analytical line intensity of every kind of element to be measured than with the linear relationship of the mass concentration of corresponding element to be measured, with
The analytical line intensity ratio of every kind of element to be measured is ordinate (Y-axis), and the mass concentration of corresponding element to be measured is abscissa (X
Axis), it calculates separately to obtain the regression equation of the standard working curve of 5 kinds of elements to be measured.
Then, ICP-AES detection then by sample solution in step 1 is carried out, by every kind of member to be measured in the sample solution of acquisition
The analytical line intensity ratio of element substitutes into the regression equation of the standard working curve of corresponding element to be measured, and according to phase in standard solution
The mass concentration of corresponding element to be measured in sample solution is calculated in the known quality concentration for answering element to be measured.For ICP-
Instrument working parameter, according to the content and property of each element, the element to be measured recommended from instrument software spectral line library is arranged in AES
In spectral line, several sensitive lines is selected to carry out spectral line screening, measures each element content.
The instrument testing conditions of ICP-AES are as follows: RF transmission power: 1150KW；Cooling air (plasma (orifice) gas): argon gas；It is cooling
Gas (plasma (orifice) gas) flow: 12L/min；Atomization gas (carrier gas): argon gas；Atomization gas (carrier gas) flow: 0.7L/min；Assist gas:
Argon gas；Secondary air amount: 0.5L/min；Sample lifting capacity: 2mL/min；Observed pattern: vertical；Observed altitude: 12mm；It rinses
Time: 40s；The shortwave time of integration: 20s；The long wave time of integration: 5s.
The analysis of line wavelength of element is tested in ICP-AES are as follows: silicon (Si): 251.611nm；Manganese (Mn): 257.610nm；Molybdenum
(Mo): 204.598nm；Iron (Fe): 259.940nm, tungsten (W): W content >=1wt%, 207.911nm, W content < 1wt%,
209.475nm。
Embodiment 3
By the preparation method of step 2 Plays solution in embodiment 1, element to be measured, configuration one are added in matrix solution
The standard solution of serial various concentration is measured, with the analytical line intensity of every kind of element to be measured than with corresponding element to be measured
The linear relationship of mass concentration draws corresponding standard working curve.Its range of linearity, unary linear regression equation, phase relation
Number is shown in Table 3.
Meanwhile replication blank solution 10 times, taking concentration value corresponding to 3 times of standard deviations is quantitative detection limit, is obtained
The quantitative detection limit obtained is shown in Table 2.
2 range of linearity of table and detection limit
Y: analytical line intensity ratio；X: mass concentration
As shown in Table 2, the working curve of 5 kinds of elements is linear good in certain range of linearity, correlation coefficient r2?
Not less than 0.9995.Meanwhile measuring method sensitivity with higher, quantitative detection limit is no more than 0.013%.
Embodiment 4
Respectively in the cobalt-base alloys sample of known content, silicon, manganese, molybdenum, iron, the tungsten of known concentration is added, by embodiment 2
Middle testing conditions, carry out sample pre-treatments and ICP-AES is analyzed, and calculate its rate of recovery according to scalar quantity and measured value, simultaneously
5 times (n=5) is measured in parallel to same sample solution, precision determination data is obtained, the results are shown in Table 3.As can be seen from Table 3, mesh
The average recovery rate of object is marked between 95.9-104.3%, relative standard deviation (RSD) illustrates the method for the present invention less than 1%
The rate of recovery and repeatability are satisfactory, are able to satisfy detection needs completely.
3 the method for the present invention rate of recovery of table and precision
| Element | Average sample content (%) | Average scalar quantity (%) | Average detectable value (%) | Average recovery rate (%) | RSD (%), n=5 |
| Silicon | 1.588 | 0.5 | 0.4795 | 95.9 | 0.40 |
| Manganese | 0.587 | 0.5 | 0.5117 | 102.3 | 0.85 |
| Molybdenum | 5.507 | 0.5 | 0.517 | 103.4 | 0.49 |
| Iron | 0.957 | 0.5 | 0.5027 | 104.3 | 0.92 |
| Tungsten | 0.054 | 0.05 | 0.0492 | 98.4 | 0.93 |
Embodiment 5
From the continuous mode and mathematical model of inductively coupled plasma emission spectrography measurement All of elements in Cobalt-based Alloy
Analysis, the uncertainty of measured value depend on the uncertainty of input quantity.The functional relation of measured value ω and input quantity such as following formula:
In formula:
ω --- the mass fraction of element in sample, numerical value is with 102Or % is indicated；
V --- the numerical value of test solution volume, unit are milliliter (mL)；
The numerical value of m --- sample amount, unit are gram (g)；
ρ --- the numerical value of concentration of element in the sample solution be calculated by calibration curve, unit are percentage (%)
Uncertainty source include the uncertainty of measurement reproducibility, the uncertainty of test solution volume, sample amount not really
The uncertainty of concentration of element in fixed degree and test solution.Wherein the uncertainty of concentration of element includes that calibration curve is linear again in test solution
The uncertainty of fitting, the uncertainty of concentration of standard solution and the uncertainty for pipetting standard solution volume.It will be above-mentioned not true
The uncertainty evaluation that fixed degree synthesis obtains Si, Mn, Mo, Fe, W each element the results are shown in Table 4.
The element determination result uncertainty evaluation to be measured of table 4
| Element | Si | Mn | Mo | Fe | W |
| Uncertain evaluation | 1.588±0.016 | 0.587±0.020 | 5.506±0.034 | 0.957±0.015 | 0.0519±0.0036 |
As shown in Table 4, the systematic error of measuring method and accidental error meet range as defined in uncertainty in the present invention,
It is able to satisfy detection needs completely.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention
It is interior.
Claims (10)
1. a kind of method of silicon, manganese, molybdenum, iron, W content in measurement cobalt-base alloys, comprising the following steps:
1) sample pre-treatments: weighing cobalt-base alloys sample, and digestion agent is added, and carries out cooling after micro-wave digestion, adds saturation boron
After acid solution carries out confined reaction, transfer, constant volume obtain sample solution；
2) preparation of standard solution: matrix solution is chosen, element to be measured is added, is made into standard solution；
3) measure: it is former that sample solution in the standard solution of step 2) preparation, step 1) is carried out inductively coupled plasma body respectively
The detection of sub- emission spectrometer, quantify using calibration curve method, and silicon in acquisition sample solution, manganese, molybdenum, iron, wolfram element contain
Amount.
2. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In in step 1), the digestion agent is the mixed solution of hydrochloric acid, nitric acid, hydrofluoric acid；The mixing of the hydrochloric acid, nitric acid, hydrofluoric acid
In solution, the ratio between the volume that the hydrochloric acid, nitric acid are added is 3:1~10:1, and it is≤2mL that volume, which is added, in the hydrofluoric acid, described
Hydrochloric acid, nitric acid, hydrofluoric acid total volume be 8~30mL.
3. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In in step 1), the ratio between the volume mL that the quality g and digestion agent that the cobalt-base alloys sample is added are added is 1:100~1:
350。
4. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In, in step 1), the temperature program of the micro-wave digestion are as follows: initial temperature is 20~30 DEG C, with the heating-up time of 10~15min
100~120 DEG C are risen to, 15~20min is kept；140~150 DEG C are risen to again with the heating-up time of 10~15min, keep 15~
30min。
5. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In in step 1), the saturation boric acid solution is the boric acid aqueous solution that mass percent concentration is 4-6wt%；The saturation boron
The ratio between volume that hydrofluoric acid is added in acid solution and digestion agent is 4:1~10:1.
6. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In in step 1), the time of the confined reaction is 25-35min.
7. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In, in step 2), the matrix solution be hydrochloric acid, nitric acid, chromium stock solution, cobalt stock solution mixed solution；The matrix solution
In, the ratio between the volume that the hydrochloric acid, nitric acid, chromium stock solution, cobalt stock solution are added is 3~10:1:1~3:1~1.5.
8. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In, in step 2), in the standard solution, concentration≤5.00wt% of the element silicon, the concentration of the manganese element is≤
4.00wt%, concentration≤8.00wt% of the molybdenum element, concentration≤5.00wt% of the ferro element, the wolfram element it is dense
Degree≤8.00wt%.
9. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In, in step 3), the instrument testing conditions of the inductively coupled plasma atomic emission spectrometer are as follows:
RF transmission power: 950,1150,1350,1500 or 1600KW；Cooling air: argon gas；Cooling gas flow: 10-20L/min；
Atomization gas: argon gas；Atomization gas flow: 0.5-1.5L/min；Assist gas: argon gas；Secondary air amount: 0.1-2L/min；Sample mentions
Rising amount: 1-5mL/min；Observed pattern: horizontal or vertical；Observed altitude: 5-15mm；Washing time: 30-50s；When shortwave integrates
Between: 15-25s；The long wave time of integration: 3-10s.
10. the method for silicon, manganese, molybdenum, iron, W content, feature exist in a kind of measurement cobalt-base alloys according to claim 1
In, in step 3), the analysis of line wavelength of the inductively coupled plasma atomic emission spectrometer are as follows: silicon: 251.611,
288.158nm；Manganese: 257.610,259.373nm；Molybdenum: 204.598,202.032nm；Iron: 259.940,238.204nm, tungsten:
207.911、209.475nm。
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