CN107315001B - A kind of method of content of niobium in measurement titanium-niobium alloy - Google Patents
A kind of method of content of niobium in measurement titanium-niobium alloy Download PDFInfo
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- CN107315001B CN107315001B CN201610269117.9A CN201610269117A CN107315001B CN 107315001 B CN107315001 B CN 107315001B CN 201610269117 A CN201610269117 A CN 201610269117A CN 107315001 B CN107315001 B CN 107315001B
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Abstract
The present invention discloses a kind of method for measuring content of niobium in titanium-niobium alloy, step are as follows: prepares Ti45Nb sample solution；Ti45Nb sample solution is taken, is developed the color with PAR solution；The nm wavelength of 520nm ~ 530 on spectrophotometer, measures the absorbance of chromophoric solution；Prepare niobium standard solution solution；Prepare titanium bottom liquid；Prepare series standard solution, for establish the niobium concentration of curve from 0.00% to 0.25 × 10‑3% corresponds to the niobium concentration in alloy sample from 0% to 50%；It establishes working curve: developing the color to the series standard solution of S6, measure absorbance value, establishing by abscissa, absorbance value of concentration is the working curve of ordinate；The absorbance value measured after the dissolution of Ti45Nb sample is developed the color is counter on the working curve of foundation to find corresponding concentration value, obtains the content of niobium in Ti45Nb memory alloy material with this.The result that the method for the present invention color stability, working curve are satisfactory, data redundancy is good.
Description
Technical field
The present invention relates to chemical analysis methods, contain more specifically to metal niobium in a kind of Their Determination by Spectrophotometry alloy
The method of amount.
Background technique
Memory alloy material has NiTiNb, Ti45Nb etc., in order to guarantee the reversible transition performance of material, adds in the material
The elements such as the niobium Nb of high-content, titanium Ti, nickel, this is rare in other conventional materials.These elements contain in the material
The height variation of amount directly will affect the performance of material.Therefore, the accurate of these elements in every batch of material has only accurately been grasped
Content can just be further ensured that the physical property and processing performance of material.But it is domestic for measuring memorial alloy at present
Without unified, mature detection technique, urgent need studies detection technique by NiTiNb, Ti45Nb etc..
Especially to the detection technique for containing 40.0%~50.0% high-content niobium in Ti45Nb memory alloy material, at present state
It is inside and outside to be showed no disclosed applicable standards.General disclosed detection technique, both for ferro-niobium, tantalum ore stone, niobium ore, steel
And in alloy etc. niobium detection method, the limitation of detection method are as follows: the 1) content of niobium that existing detection method usually detects
For constant, it is unable to the content of niobium that detection level is up to 40.0%~50.0%.As HB 5220.34-2008 " inhale by chlorfomphehol C
Light photometry measurement content of niobium " can only measure in high temperature alloy 0.10%~3.00% content of niobium；GB/T4698.22-1996
" 5-Br-PADAP spectrophotometry measures niobium amount " can only measure in titanium or titanium alloy 0.20%~3.00% content of niobium；GB/
The niobium that T 223.38-1985 " ionic energy transfer-gravimetric detemination niobium amount " can only measure in steel 1.00%~5.00% contains
Amount；It is that the niobium of 0.005 %~1.3% contains as ISO 9441 " PAR spectrophotometry measures niobium amount " can only measure content in steel
Amount；It is 0.01 % as Γ Ο C Τ 12361 " PAR photometry measures niobium amount " can only measure content in steel alloy and high-alloy steel
The content of niobium of~8.00 %.2) type of the target material of existing detection method detection all only has steel, steel alloy, niobium minerals
Stone etc., these material categories and Ti45Nb memory alloy material composition have very big difference, cannot directly use.Such as HB
" 5220.33-2008 high temperature alloy chemical analysis method tetraphenylarsonium chloride hydrochloride gravimetric detemination content of niobium ", measurement range >
1.00%, but because target material is high temperature alloy, the chemical analysis and this bianry alloy composition difference of Ti45Nb of high temperature alloy
Very big, detection method cannot be applicable in.
Since the limitation of the current domestic prior art constrains promoting the use for memory alloy material, it can be seen that research
Out a kind of unification, precision is high, reproducible detection method is come in Accurate Determining Ti45Nb memory alloy material containing 40.0%
~50.0% high-content niobium, the development for being not only conducive to new material more can guarantee utilization of the material on product.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides the measurement Ti45Nb memory that a kind of precision is high, reproducible
The chemical analysis detection method of high-content niobium in alloy material.
To solve above-mentioned deficiency of the prior art, the present invention are achieved through the following technical solutions:
The method of content of niobium, step in a kind of measurement titanium-niobium alloy are as follows:
S1 prepares Ti45Nb sample solution: weighing Ti45Nb sample, dissolves；
S2 takes Ti45Nb sample solution, is developed the color with PAR solution, and PAR is 4- (2- pyridylazo)-resorcinol or 1- (2-
Pyridylazo)-resorcinol；
520nm ~ 530 nm wavelength of the S3 on spectrophotometer, measures the absorbance of chromophoric solution；
S4 prepares niobium standard solution solution: weighing pure niobium sample, dissolves；
S5 prepares titanium bottom liquid: weighing pure titanium sample, dissolves；
S6 prepares series standard solution: pipetting 5.00mL titanium bottom liquid respectively in different capabilities bottle, then successively in volumetric flask
In be separately added into the different amounts of niobium standard solution of 0 mL to 5 mL, for establish the niobium concentration of curve from 0.00 % to 0.25 ×
10-3 The series of standards solution of % corresponds to the niobium concentration in alloy sample from 0% to 50%；
S7 establishes working curve: carrying out to the series standard solution of S6 according to the same method of same Ti45Nb sample solution
Colour developing measures the absorbance value of the series standard solution respectively on spectrophotometer, establishes using concentration as abscissa, absorbance
Value is the working curve of ordinate；
The absorbance value that S8 is measured after the dissolution of Ti45Nb sample develops the color is counter on the working curve that S7 is established to find corresponding
Concentration value, the content of niobium in Ti45Nb memory alloy material is obtained with this.
The method that the S1 prepares Ti45Nb sample solution are as follows:
0.09g ~ 0.20g sample is weighed, is placed in 150mL polytetrafluoroethylene beaker
5mL ~ 10mL concentrated nitric acid is added, the dense hydrofluoric acid of the mL of 1 mL ~ 2 is added dropwise, low-temperature heat to sample is dissolved, and it is slightly cold,
The sulfuric acid solution that the mL of 20 mL ~ 25 is mixed by 1 part of pure water and 1 part of concentrated sulfuric acid, low-temperature heat to solution is added
Volume is about 20 mL,
It moves into 250mL beaker, is heated to emitting the 1st sulphoxylic acid cigarette about 3 ~ 4min, it is slightly cooling to remove beaker, then into beaker
It is blown into a small amount of water, is heated to emitting the 2nd sulphoxylic acid cigarette about 2 ~ 3min, it is cooling, to catch up with most F-Ion and NO3 -Ion,
20 mL concentration, 250 g/L tartaric acid solution is added, 5 mL concentration, 100 g/L ammonium fluoride solution boils 2-3 minutes,
10 mL saturation boric acid solution is added to continue to boil, is cooled to room temperature,
Test solution is moved into 500 mL volumetric flasks, scale is diluted with water to, shakes up.
PAR coloration method in the S2 are as follows:
The dissolved sample solution of 5.00mL accurately is pipetted in 200mL volumetric flask, and potassium pyrosulfate 5g/L and winestone is added
5.0 mL of mixed liquor of 62.5 g/L of acid, adds 250 g/L tartaric acid solution of the mL of 8.0mL ~ 12.0 concentration, place 3 min~
5 min, addition mix hydrochloric acid solution 10 mL ~ 15 mL by 1 part of pure water and 1 part of concentrated hydrochloric acid and form color acidity condition, add
Enter 25 g/L solution of the mL EDTA of 4.0 mL ~ 6 concentration, 10.00 mL concentration, 2 g/L PAR solution is accurately added after mixing, uses
Water is diluted to scale, shakes up；It is placed in the min of 50 min ~ 60 in 60 ± 5 DEG C of hot water, is taken out, water cooling to room temperature, from solution constant volume
Start to calculate, spectrophotometry measurement is carried out after three hours ~ five hours.
In the S2, PAR solution methods are prepared are as follows: weigh 1.0 g PAR, be placed in 250 mL beakers, 20 mL are added
10 mL sodium hydroxides (100 g/L) is added dropwise to dissolving in pure water, is diluted with water to 500 mL, mixes.
Light splitting degree measures extinction at the nm wavelength of the 520nm on spectrophotometer ~ 530, with 1cm ~ 2cm cuvette
Angle value.
It prepares niobium standard solution (concentration is 0.10 g/L): weighing pure 0.1000 g of niobium powder and be placed in porcelain crucible, be added 5.0
The commercially available potassium pyrosulfate solid of g is placed in 800 DEG C of high temperature furnace and melts 10 minutes, and frit is with 200 mL tartaric acid solutions (250
G/L it) leaches, moves into 1000 mL volumetric flasks, be diluted with water to scale, shake up.
It establishes Titanium base matching working curve: titanium valve 0.050g ~ 0.055g without niobium is weighed, according to same
The identical method dissolution of Ti45Nb sample prepares titanium bottom liquid.The 5.00mL titanium bottom liquid number part is pipetted respectively, is respectively placed in several 200
In the volumetric flask of mL, the niobium standard solution [0.10 of the mL of 0.00 mL ~ 5.00 is successively separately added into several volumetric flasks
Mg/mL], the niobium concentration of curve is established from 0.00 % to 0.25 × 10-3 The series of standards solution of % (corresponds to alloy sample
In niobium concentration from 0% to 50%).It develops the color, is dividing according to the same method of same Ti45Nb sample to the series standard solution
The single absorbance value for measuring the series standard solution on light photometer respectively, establishing concentration is abscissa, and absorbance value is vertical
The corresponding working curve of coordinate.
The absorbance value measured after the dissolution of Ti45Nb sample is developed the color is counter on the working curve of foundation to find corresponding dense
Angle value measures the content of niobium in Ti45Nb memory alloy material with this.
Compared with prior art, the present invention has the advantages that
1. method of the present invention is because fully considered that content is up to the influence of 50% or so titanium, using " nitric acid-hydrogen
Fluoric acid-sulfuric acid " dissolution method can quickly dissolve Ti45Nb material, and sample solution is clarified and stablized, and the prior art should all be
All very low and that the impurity such as tungstenic, molybdenum, zirconium, tantalum the are more alloy of the niobium contents such as steel and titaniferous amount is dissolved, is mostly to use
Hydrochloric acid-nitric acid dissolution, or hydrogen peroxide oxidation is added, niobium and tantalum are precipitated with arsenobenzene acid；Or melted in Muffle furnace high temperature,
But these methods are not because accounting for titanium elements, for dissolving Ti45Nb material, sample perhaps dissolves not exclusively or when dissolution
Between it is long, or become turbid, not can be carried out subsequent analysis.
2. titanium solution when establishing working curve, is added in method of the present invention in niobium standard solution, titanium-based is carried out
Body matches working curve, eliminates interference of the matrix element Ti to Nb in Ti45Nb material, the test for niobium, and relative standard is inclined
Difference is less than 1.0%, and the prior art does not all account for the interference problem and high-content niobium that content is up to 50% or so titanium elements
Measurement need, therefore the prior art either uses high purity iron perhaps steel sample is covered as matrix or curve when establishing curve
The niobium concentration highest of lid is only to 8% or so.The survey of high-content niobium in Ti45Nb material can not be carried out with the curve that the prior art is established
It is fixed.
3. emphasis paratartaric acid dosage of the present invention is studied, it is believed that tartaric acid be mainly used for be complexed niobium element and
It participates in niobium and PAR complexing develops the color.Also " in hydrochloric acid medium niobium and PAR and tartaric acid are mentioned in prior art Γ Ο C Τ 12361
Ion forms colored complex, and the influence of coexistence elements is sheltered with EDTA to be eliminated ", but content of niobium in the sample of prior art research
Highest is only to 8% or so, therefore the amount that ammonium tartrate or tartaric acid is added is seldom, generally only reaches the g/L of 1g/L in developing solution ~ 5.
And for Ti45Nb material, because the content of niobium is very high, enough tartaric acid need to be added niobium is complexed, so the present invention couple
The dosage of tartaric acid is studied, show except to sample (0.09g ~ 0.20g) dissolution after need be added 20 mL tartaric acid solutions
(250 g/L) outside, needs to add the mL of 8.0mL ~ 12.0 tartaric acid solution (250 in point solution of the subsequent colour developing of progress taken
G/L), reach developing solution mesotartaric acid content 12.5g/L ~ 17.5g/L, niobium element is sufficiently complexed.The present invention is than existing skill
Art increases several times or decades of times in the dosage of tartaric acid, and available color stability, working curve be satisfactory, Data duplication
The good result of property.
4. emphasis of the present invention also studies EDTA dosage, the effect of EDTA is to eliminate solution to shelter complexing
In other ions such as the titanium that coexists interference." the influence EDTA of coexistence elements is also mentioned in prior art Γ Ο C Τ 12361
Masking is eliminated ", but the prior art is mainly for the measurement of steel, primary concern is that the impurity such as tungsten, molybdenum, zirconium, tantalum in steel
Elimination, except be added arsenobenzene acid or tannin or crystal violet and impurity co-precipitation in addition to, the amount of the EDTA of addition generally only has
0.17g/L ~0.3g/L.The present invention is directed Ti45Nb bianry alloy, there is no the impurity such as tungsten, molybdenum, zirconium, tantalum in alloy, and titanium
Content it is very high, therefore only can reach masking complexing well with the dosage for changing EDTA and eliminate titanium and other coexistence elements
Interference effect, the present invention in EDTA most suitable additional amount be 0.5g/L ~ 0.75g/L.
5. the present invention is investigated the preparation and dosage of color developing agent PAR.In the prior art to the use of PAR color developing agent, have
Using 4- (2- pyridylazo)-resorcinol sodium salt, have using 4- (2- pyridylazo)-resorcinol or 1- (2- pyridine idol
Nitrogen)-resorcinol, both for the colour developing of low content niobium, the dosage in developing solution is generally for the method and dosage of preparation
0.02g/L~0.06g/L.And if present invention research thinks that a large amount of dehydrated alcohols or the hydroxide of high concentration need to be used using PAR sodium salt
Sodium is dissolved, and the stability influence of the solution of chromogenic assay niobium subsequent for Ti45Nb material is larger, should reduce sodium hydroxide
Use, therefore the present invention use 4- (2- pyridylazo)-resorcinol or 1- (2- pyridylazo)-resorcinol for colour developing
Agent, and the additional amount of PAR in developing solution should be increased so that colored complex can be sufficiently formed with niobium and winestone acid ion, the present invention
In PAR most suitable additional amount be 0.1g/L.
Detailed description of the invention
Fig. 1 is the standard curve of the embodiment of the present invention 1
Fig. 2 is the standard curve of the embodiment of the present invention 2
Fig. 3 is the standard curve of the embodiment of the present invention 3.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings.
Capital equipment used by the embodiment of the present invention, reagent, solution are as follows:
1. test apparatus: spectrophotometer.
2. test reagent
2.1 nitric acid, about 1.42 g/mL of ρ.
2.2 sulfuric acid, about 1.84 g/mL of ρ.
2.3 hydrofluoric acid, ρ about 1.15 g/mL.
2.4 hydrochloric acid solutions are mixed by 1 part of pure water and 1 part of concentrated hydrochloric acid.
2.5 sulfuric acid solutions are mixed by 1 part of pure water and 1 part of concentrated sulfuric acid.
2.6 tartaric acid solutions: 250 g/L.
2.7 ammonium fluoride solutions: 100 g/L.
2.8 boric acid: saturated solution.
2.9 EDTA solution: 25 g/L.
2.10 sodium hydroxides: 100 g/L.
2.11 potassium pyrosulfates: solid.
2.12 PAR solution, 2 g/L.
PAR is known as [4- (2- pyridylazo)-resorcinol] or [1- (2- pyridylazo)-resorcinol].Weigh 1.0 g
PAR is placed in 250 mL beakers, and 20 mL water are added, 10 mL sodium hydroxides (100 g/L) is added dropwise to dissolving, are diluted with water to
500 mL are mixed.
2.13 niobium standard solution, 0.10 mg/mL.
It weighs pure 0.1000 g of niobium powder to be placed in porcelain crucible, 5.0 g potassium pyrosulfates (solid) is added, are placed in 800 DEG C of height
It is melted 10 minutes in warm furnace, frit is moved into 1000 mL volumetric flasks, used water with 200 mL tartaric acid solutions (250 g/L) leaching
It is diluted to scale, is shaken up.
2.14 mixed liquor
5.0 g potassium pyrosulfates (solid) are weighed in porcelain crucible, is placed in 800 DEG C of high temperature furnace and melts 10 minutes, frit
With 200 mL tartaric acid solutions (250 g/L) leaching, 1000 mL volumetric flasks are moved into, scale is diluted with water to, shakes up.
Embodiment 1
3 sample samples
0.0998g sample sample is weighed, 0.0001g is accurate to.
The preparation of 4 test solutions
4.1 are placed in sample (3) in 150 mL polytetrafluoroethylene beakers, and 5 mL nitric acid (2.1) are added, and 1 mL hydrogen is added dropwise
Fluoric acid (2.3) low-temperature heat to sample dissolves, slightly cold, 20 mL sulfuric acid (2.5) is added, low-temperature heat to liquor capacity is about 20
ML is removed, and is moved into 250mL beaker, is heated to emitting sulfuric acid cigarette, is heated to emitting the 1st sulphoxylic acid cigarette about 3 ~ 4min, removes beaker slightly
It is cooling, then a small amount of water is blown into beaker, it is heated to emitting the 2nd sulphoxylic acid cigarette about 2 ~ 3min, it is cooling, it is molten that 20 mL tartaric acid are added
Liquid (2.6), 5 mL ammonium fluoride solutions (2.7), boils 2 ~ 3 minutes, removes, and 10 mL saturation boric acid solution (2.8) is added and continues to boil
Boiling, is cooled to room temperature, and test solution is moved into 500 mL volumetric flasks, scale is diluted with water to, shakes up.
4.2 developing solutions: accurately pipetting 5.00 mL test solutions (4.1) in 200 mL volumetric flasks, and 5.0 mL mixed liquors are added
(2.14), 8.0 mL tartaric acid solution (2.6) places the min of 3 min~5, and 10 mL hydrochloric acid (2.4), 4.0 mL EDTA are added
Solution (2.9) is accurately added 10.00 mL PAR solution (2.12), is diluted with water to scale, shakes up after mixing.It is placed in 60 ± 5
DEG C hot water in 60 min, take out, water cooling to room temperature calculates since solution constant volume, start to measure after three hours.
4.3 reference liquids: reference liquid identical as working curve.
5 measurements
Developing solution (4.2) are moved into 1.0 cm cuvettes, with reference liquid (4.3) for reference, are surveyed at 530 nm wavelength
Absorbance is measured, niobium amount is checked in from working curve.(in actual measurement, use the extinction for the sample that 722 spectrophotometers obtain
Angle value is 0.388.)
The drafting of 6 working curves
6.1 weigh 0.050 g of titanium valve without niobium carries out according to 4.1.
6.2 pipette 5.00 several parts of mL solution (6.1), are respectively placed in the volumetric flask of several 200 mL, sequentially add
0.00,1.00,2.00,3.00,4.00,5.00 mL niobium standard solution (2.13), different volumes mixed liquor (2.14), which are added, to be made respectively
It is consistent with curve highest point to select mixed liquor dosage, 8.0 mL tartaric acid solutions (2.6) are added, places the min of 3 min~5, is added
10 mL hydrochloric acid (2.4), 4.0 mL EDTA solution (2.9), are accurately added 10.00 mL PAR solution (2.12), use water after mixing
It is diluted to scale, is shaken up.60 min in 60 ± 5 DEG C of hot water are placed in, are taken out, water cooling to room temperature is calculated since solution constant volume,
Start to measure after three hours.It is operated by 5 steps.Using the solution that niobium is not added as reference liquid, absorbance is measured.
For 6.3 absorbances measured using every bottle of solution as ordinate Y, the content of niobium (mg) in corresponding solution is abscissa,
Working curve is drawn, sees that Fig. 1, obtained linear equation are y=0.0085x, R2For the linearly dependent coefficient of working curve.
The calculating of 7 analysis results
The mass fraction ω of niobium is calculated by formula (1), numerical value is indicated with %:
In formula:
m1-- the niobium amount checked in from working curve, unit are milligram (mg)；
M -- the quality of contained sample in developing solution, unit are milligram (mg).
The absorbance value that the sample measures is found into niobium amount m on working curve (6.3)1, it substitutes into formula and calculates, finally
It is 45.74% to the content of niobium in the sample.
Embodiment 2
3 sample samples
0.1998 g sample sample is weighed, 0.0001 g is accurate to.
The preparation of 4 test solutions
4.1 are placed in sample (3) in 150 mL polytetrafluoroethylene beakers, and 10 mL nitric acid (2.1) are added, and 2 mL hydrogen are added dropwise
Fluoric acid (2.3) low-temperature heat to sample dissolves, slightly cold, 25 mL sulfuric acid (2.5) is added, low-temperature heat to liquor capacity is about 20
ML is removed, and is moved into 250mL beaker, is heated to emitting sulfuric acid cigarette, is heated to emitting the 1st sulphoxylic acid cigarette about 3 ~ 4min, removes beaker slightly
It is cooling, then a small amount of water is blown into beaker, it is heated to emitting the 2nd sulphoxylic acid cigarette about 2 ~ 3min, it is cooling, it is molten that 20 mL tartaric acid are added
Liquid (2.6), 5 mL ammonium fluoride solutions (2.7), boils 2 ~ 3 minutes, removes, and 10 mL saturation boric acid solution (2.8) is added and continues to boil
Boiling, is cooled to room temperature, and test solution is moved into 500 mL volumetric flasks, scale is diluted with water to, shakes up.
4.2 developing solutions: accurately pipetting 5.00 mL test solutions (4.1) in 200 mL volumetric flasks, and 5.0 mL mixed liquors are added
(2.14), 12.0 mL tartaric acid solution (2.6) places the min of 3 min~5, and 15 mL hydrochloric acid (2.4), 6.0 mL EDTA are added
Solution (2.9) is accurately added 10.00 mL PAR solution (2.12), is diluted with water to scale, shakes up after mixing.It is placed in 60 ± 5
DEG C hot water in 60 min, take out, water cooling to room temperature calculates since solution constant volume, start to measure after five hours.
4.3 reference liquids: reference liquid identical as working curve.
5 measurements
Developing solution (4.2) are moved into 2.0 cm cuvettes, with reference liquid (4.3) for reference, are surveyed at 520 nm wavelength
Absorbance is measured, niobium amount is checked in from working curve.(in actual measurement, use the extinction for the sample that 722 spectrophotometers obtain
Angle value is 0.118.)
The drafting of 6 working curves
6.1 weigh 0.055 g of titanium valve without niobium carries out according to 4.1.
6.2 pipette 5.00 several parts of mL solution (6.1), are respectively placed in the volumetric flask of several 200 mL, sequentially add
0.00,1.00,2.00,3.00,4.00,5.00 mL niobium standard solution (2.13), different volumes mixed liquor (2.14), which are added, to be made respectively
It is consistent with curve highest point to select mixed liquor dosage, 12.0 mL tartaric acid solutions (2.6) are added, places the min of 3 min~5, is added
15 mL hydrochloric acid (2.4), 6.0 mL EDTA solution (2.9), are accurately added 10.00 mL PAR solution (2.12), use water after mixing
It is diluted to scale, is shaken up.60 min in 60 ± 5 DEG C of hot water are placed in, are taken out, water cooling to room temperature is calculated since solution constant volume,
Start to measure after five hours.It is operated by 5 steps.Using the solution that niobium is not added as reference liquid, absorbance is measured.
For 6.3 absorbances measured using every bottle of solution as ordinate Y, the content of niobium (mg) in corresponding solution is abscissa,
Working curve is drawn, sees that Fig. 2, obtained linear equation are y=0.0084x, R2For the linearly dependent coefficient of working curve.
The calculating of 7 analysis results
The mass fraction ω of niobium is calculated by formula (1), numerical value is indicated with %:
In formula:
m1-- the niobium amount checked in from working curve, unit are milligram (mg)；
M -- the quality of contained sample in developing solution, unit are milligram (mg).
The absorbance value that the sample measures is found into niobium amount m on working curve (6.3)1, it substitutes into formula and calculates, finally
It is 7.03% to the content of niobium in the sample.
Embodiment 3
3 sample samples
0.1502g sample sample is weighed, 0.0001g is accurate to.
The preparation of 4 test solutions
4.1 are placed in sample (3) in 150 mL polytetrafluoroethylene beakers, and 8 mL nitric acid (2.1) are added, and 2 mL hydrogen are added dropwise
Fluoric acid (2.3) low-temperature heat to sample dissolves, slightly cold, 23 mL sulfuric acid (2.5) is added, low-temperature heat to liquor capacity is about 20
ML is removed, and is moved into 250mL beaker, is heated to emitting sulfuric acid cigarette, is heated to emitting the 1st sulphoxylic acid cigarette about 3 ~ 4min, removes beaker slightly
It is cooling, then a small amount of water is blown into beaker, it is heated to emitting the 2nd sulphoxylic acid cigarette about 2 ~ 3min, it is cooling, it is molten that 20 mL tartaric acid are added
Liquid (2.6), 5 mL ammonium fluoride solutions (2.7), boils 2 ~ 3 minutes, removes, and 10 mL saturation boric acid solution (2.8) is added and continues to boil
Boiling, is cooled to room temperature, and test solution is moved into 500 mL volumetric flasks, scale is diluted with water to, shakes up.
4.2 developing solutions: accurately pipetting 5.00 mL test solutions (4.1) in 200 mL volumetric flasks, and 5.0 mL mixed liquors are added
(2.14), 10.0 mL tartaric acid solution (2.6) places the min of 3 min~5, and 12 mL hydrochloric acid (2.4), 5.0 mL EDTA are added
Solution (2.9) is accurately added 10.00 mL PAR solution (2.12), is diluted with water to scale, shakes up after mixing.It is placed in 60 ± 5
DEG C hot water in 60 min, take out, water cooling to room temperature calculates since solution constant volume, start to measure after five hours.
4.3 reference liquids: reference liquid identical as working curve.
5 measurements
Developing solution (4.2) are moved into 2.0 cm cuvettes, with reference liquid (4.3) for reference, are surveyed at 530 nm wavelength
Absorbance is measured, niobium amount is checked in from working curve.(in actual measurement, use the extinction for the sample that 722 spectrophotometers obtain
Angle value is 0.645.)
The drafting of 6 working curves
6.1 weigh 0.052 g of titanium valve without niobium carries out according to 4.1.
6.2 pipette 5.00 several parts of mL solution (6.1), are respectively placed in the volumetric flask of several 200 mL, sequentially add
0.00,1.00,2.00,3.00,4.00,5.00 mL niobium standard solution (2.13), different volumes mixed liquor (2.14), which are added, to be made respectively
It is consistent with curve highest point to select mixed liquor dosage, 10.0 mL tartaric acid solutions (2.6) are added, places the min of 3 min~5, is added
12 mL hydrochloric acid (2.4), 5.0 mL EDTA solution (2.9), are accurately added 10.00 mL PAR solution (2.12), use water after mixing
It is diluted to scale, is shaken up.60 min in 60 ± 5 DEG C of hot water are placed in, are taken out, water cooling to room temperature is calculated since solution constant volume,
Start to measure after five hours.It is operated by 5 steps.Using the solution that niobium is not added as reference liquid, absorbance is measured.
For 6.3 absorbances measured using every bottle of solution as ordinate Y, the content of niobium (mg) in corresponding solution is abscissa,
Working curve is drawn, sees that Fig. 3, obtained linear equation are y=0.0144x, R2For the linearly dependent coefficient of working curve.
The calculating of 7 analysis results
The mass fraction ω of niobium is calculated by formula (1), numerical value is indicated with %:
In formula:
m1-- the niobium amount checked in from working curve, unit are milligram (mg)；
M -- the quality of contained sample in developing solution, unit are milligram (mg).
The absorbance value that the sample measures is found into niobium amount m on working curve (6.3)1, it substitutes into formula and calculates, finally
It is 30.26% to the content of niobium in the sample.
Claims (5)
1. the method for content of niobium, step in a kind of measurement titanium-niobium alloy are as follows:
S1 prepares Ti45Nb sample solution: weighing Ti45Nb sample, dissolves；
S2 takes Ti45Nb sample solution, is developed the color with PAR solution, and PAR is 4- (2- pyridylazo)-resorcinol or 1- (2- pyridine
Azo)-resorcinol；
520nm ~ 530 nm wavelength of the S3 on spectrophotometer, measures the absorbance of chromophoric solution；
S4 prepares niobium standard solution solution: weighing pure niobium sample, dissolves；
S5 prepares titanium bottom liquid: weighing pure titanium sample, dissolves；
S6 prepares series standard solution: pipetting 5.00mL titanium bottom liquid respectively in different capabilities bottle, then successively divides in volumetric flask
The different amounts of niobium standard solution of 0 mL to 5 mL is not added, for establishing the niobium concentration of curve from 0.00 % to 0.25 × 10-3 The series of standards solution of % corresponds to the niobium concentration in alloy sample from 0% to 50%；
S7 establishes working curve: it develops the color to the series standard solution of S6 according to the same method of same Ti45Nb sample solution,
Measure the absorbance value of the series standard solution respectively on spectrophotometer, foundation is by abscissa, absorbance value of concentration
The working curve of ordinate；
The absorbance value that S8 is measured after the dissolution of Ti45Nb sample develops the color is counter on the working curve that S7 is established to find corresponding dense
Angle value obtains the content of niobium in Ti45Nb memory alloy material with this；
PAR coloration method in the S2 are as follows:
The dissolved sample solution of 5.00mL accurately is pipetted in 200mL volumetric flask, and potassium pyrosulfate 5g/L and tartaric acid is added
5.0 mL of mixed liquor of 62.5 g/L adds 250 g/L tartaric acid solution of the mL of 8.0mL ~ 12.0 concentration, places 3 min~5
Min, addition mix hydrochloric acid solution 10 mL ~ 15 mL by 1 part of pure water and 1 part of concentrated hydrochloric acid and form color acidity condition, are added
25 g/L solution of the mL EDTA of 4.0 mL ~ 6 concentration is accurately added 10.00 mL concentration, 2 g/L PAR solution, uses water after mixing
It is diluted to scale, is shaken up；It is placed in the min of 50 min ~ 60 in 60 ± 5 DEG C of hot water, is taken out, water cooling to room temperature is opened from solution constant volume
Begin to calculate, spectrophotometry measurement is carried out after three hours ~ five hours.
2. a kind of method for measuring content of niobium in titanium-niobium alloy according to claim 1, which is characterized in that the S1 is prepared
The method of Ti45Nb sample solution are as follows:
0.09g ~ 0.20g sample is weighed, is placed in 150mL polytetrafluoroethylene beaker
5mL ~ 10mL concentrated nitric acid is added, the dense hydrofluoric acid of the mL of 1 mL ~ 2 is added dropwise, low-temperature heat to sample is dissolved, and it is slightly cold,
The sulfuric acid solution that the mL of 20 mL ~ 25 is mixed by 1 part of pure water and 1 part of concentrated sulfuric acid, low-temperature heat to liquor capacity is added
About 20 mL,
It moves into 250mL beaker, is heated to emitting the 1st sulphoxylic acid cigarette about 3 ~ 4min, it is slightly cooling to remove beaker, then be blown into beaker
A small amount of water is heated to emitting the 2nd sulphoxylic acid cigarette about 2 ~ 3min, cooling, to catch up with most F-Ion and NO3 -Ion,
20 mL concentration, 250 g/L tartaric acid solution is added, 5 mL concentration, 100 g/L ammonium fluoride solution boils 2-3 minutes,
10 mL saturation boric acid solution is added to continue to boil, is cooled to room temperature,
Test solution is moved into 500 mL volumetric flasks, scale is diluted with water to, shakes up.
3. a kind of method for measuring content of niobium in titanium-niobium alloy according to claim 1, which is characterized in that the S2 is prepared
PAR solution methods are as follows: weigh 1.0 g PAR, be placed in 250 mL beakers, 20 mL pure water are added, 10 mL sodium hydroxides are added dropwise
(100 g/L) is diluted with water to 500 mL to dissolving, and mixes.
4. a kind of method for measuring content of niobium in titanium-niobium alloy according to claim 1, which is characterized in that match in the S4
Niobium standard solution method processed are as follows:
It weighs pure 0.1000 g of niobium powder to be placed in porcelain crucible, the commercially available potassium pyrosulfate solid of 5.0 g is added, is placed in 800 DEG C of high temperature
It is melted 10 minutes in furnace, by frit with the leaching of 200 mL concentration, 250 g/L tartaric acid solution, moves into 1000 mL volumetric flasks, use
Water is diluted to scale, shakes up, and obtaining concentration is 0.10 g/L niobium standard solution.
5. a kind of method for measuring content of niobium in titanium-niobium alloy according to claim 1, which is characterized in that match in the S5
Titanium bottom liquid method processed are as follows:
0.09g ~ 0.20g sample is weighed, is placed in 150mL polytetrafluoroethylene beaker
5mL ~ 10mL concentrated nitric acid is added, the dense hydrofluoric acid of the mL of 1 mL ~ 2 is added dropwise, low-temperature heat to sample is dissolved, and it is slightly cold,
The sulfuric acid solution that the mL of 20 mL ~ 25 is mixed by 1 part of pure water and 1 part of concentrated sulfuric acid, low-temperature heat to liquor capacity is added
About 20 mL,
It moves into 250mL beaker, is heated to emitting the 1st sulphoxylic acid cigarette about 3 ~ 4min, it is slightly cooling to remove beaker, then be blown into beaker
A small amount of water is heated to emitting the 2nd sulphoxylic acid cigarette about 2 ~ 3min, cooling, to catch up with most F-Ion and NO3 -Ion,
20 mL concentration, 250 g/L tartaric acid solution is added, 5 mL concentration, 100 g/L ammonium fluoride solution boils 2-3 minutes,
10 mL saturation boric acid solution is added to continue to boil, is cooled to room temperature,
Test solution is moved into 500 mL volumetric flasks, scale is diluted with water to, shakes up.
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| "PAR分光光度法测定合金钢中的铌";魏奎钧;《厂矿试验室》;19641231(第12期);第62-63页 * |
| "Spectrophotometric determination of niobium in Zirconium, Titanium and Other Metals with 4-(2-Pridylazo)resorcinol";D.F.Wood 等;《Analyst》;19680331;第93卷;第131-141页 * |
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