CN102650614A

CN102650614A - Method for determining content of boron nitride in steel

Info

Publication number: CN102650614A
Application number: CN2012101553277A
Authority: CN
Inventors: 丁美英; 石林; 田永生; 刘淼
Original assignee: Baotou Iron and Steel Group Co Ltd
Current assignee: Baotou Iron and Steel Group Co Ltd; Inner Mongolia Baotou Steel Union Co Ltd
Priority date: 2012-05-18
Filing date: 2012-05-18
Publication date: 2012-08-29

Abstract

The invention relates to a method for determining the content of boron nitride in steel, which belongs to the technical field of analytical chemistry. The mixed acid of nitric acid and hydrochloric acid is used for separating solid solution boron and other forms of borides, and boron nitride is quantitively retained; and the boron nitride is resolved by the nitric acid and perchloric acid. The boron nitride is diluted to a regulated volume, and the content of boron in the boron nitride is determined by an inductive coupling plasma mass spectrometry. The method can be used for accurately and quickly determining and converting the content of the boron nitride in the steel.

Description

A kind of nitrogen in steel boron Determination on content method

One, technical field

The invention belongs to technical field of analytical chemistry, relate to a kind of quantitative analysis tech of nitrogen in steel boron.

Two, background technology

Boron is alloying element important in the steel, and boron mainly exists with forms such as solid solution attitude, carbonide and nitride in steel, and different shape is different to the performance impact of steel, and boron nitride has harmful effect to the performance of steel, and it is extremely important therefore accurately to measure its content.At present, nitrogen in steel boron does not still have analytical approach, and we have invented this method through experiment.

Three, summary of the invention

The objective of the invention is to disclose a kind of nitrogen in steel boron Determination on content method, utilize this method can accurately measure the content of nitrogen in steel boron.

At first, confirm the span of correlation parameter through experiment and to the influence factor of assay method.

1, Instrument working parameter

ELAN DRC-e ICP-MS (U.S. PE company)

The running parameter of ICP-MS instrument is single charge ion intensity and multi-atomic ion intensity such as the oxide that possibly produce interference, sulfide of influence element to be measured directly.For this reason, before measuring, the Mg, In, Ba, Ce, U mixed standard solution (tuning solution) that at first adopts 10 μ g/mL carries out parameter corrections such as mass calibration, resolution are tuning, lens voltage detecting device to mass spectrometer.Utilize the Tuning and the Optimize function of instrument, be optimized and obtain Instrument working parameter, see table 1.

Table 1: Instrument working parameter

2, the selection of instrument test condition

With the boron standard solution that contains perchloric acid, carry out the condition test of power, atomizer flow, secondary air amount etc. successively, the result shows:

1) along with the increase (increasing to 1300W from 900W) of power, line strength of boron increases, and power is when 1050W～1200W, and it is maximum that the intensity of boron reaches.

2) plasma gas flow rate increases to 18L/min from 11L/min, and line strength of boron does not have significant change;

3) the atomizer flow increases to 1.10L/min from 0.70L/min, and the intensity of boron also changes thereupon, and is interval at 0.80L/min～0.95L/min, and the response of boron is maximum;

4) the secondary air amount increases to 1.7L/min from 0.8L/min, and line strength of boron does not have significant change.

According to power, atomizer flow, secondary air amount, plasma gas flow rate experiment; It is test condition that this method is selected the related data that line strength is big, background is low; Selection result is: power 1100W, atomizer flow 0.80L/min, secondary air amount 1.2L/min, plasma gas flow rate 15L/min.

3, isotopic selection

The coordination of boron have ¹⁰B, ¹¹B is in mensuration ¹¹Therefore the stable and good linearity of the measured value of B is selected ¹¹B is an analytical line.

4, the selection of sample size

Divide another name 0.5000g, 1.0000g, 2.0000g BT100H steel appearance, Q690 steel appearance each some parts, carry out sample dissolution, suction filtration, washing, add nitric acid respectively, perchloric acid decomposes boron nitride by experimental technique, constant volume, mensuration then, the result sees table 2.

Table 2: definite % of sample weighting amount

It is thus clear that sample weighting amount all can accurately be measured the content of boron nitride at 0.5000g～2.0000g.In order to reduce error at measurment, this method sample size is 1.0000g～2.0000g.

5, the boron nitride separation condition confirms

Claim each some parts of 1.0000gBT100H steel appearance, Q690 steel appearance, in the 150mL quartz beaker, each adds 20mL water, adds the nitration mixture heating for dissolving of different amounts more respectively, decomposes the boride of other form, measures by experimental technique, and the result sees table 3.

Table 3: definite % of boron nitride separation condition

It is thus clear that two kinds of nitration mixture can dissolve the boride of other form fully, quantitatively keep boron nitride.

6, the boron nitride decomposition condition confirms

Claim each some parts of 1.0000gBT100H steel appearance, Q690 steel appearance, in the 150mL quartz beaker, add 20mL water, 10mL hydrochloric acid, 10mL nitric acid heating for dissolving respectively, decompose the boride of other form.

(1) in glass sand core funnel suction filtration, the washing of shop filter membrane, carry out the mensuration of boron in the boron nitride by experimental technique, the result sees table 5.

Carry out sample dissolution, suction filtration, washing by experimental technique, the nitric acid, the perchloric acid that add different amounts respectively decompose boron nitride, constant volume, mensuration then, and the result sees table 4.

Table 4: the definite % that does not contain filter paper boron nitride decomposition condition

The above results shows that the boron nitride that does not contain filter paper adopts 3mLHNO ₃+ 3mLHClO ₄Can decompose boron nitride fully.

(2) glass funnel of quantitative filter paper filters, washing with being covered with at a slow speed; In the time of in moving into the 150mL quartz beaker, the part that does not have the boron nitride deposition on the filter paper is torn off, will precipitate quartz beaker again together with filter paper immigration 150mL; The abundant carbonization filter paper of nitric acid that adds different amounts; The perchloric acid that adds different amounts again decomposes boron nitride, and through measuring, the result sees table 5.

Table 5: the definite % that contains filter paper boron nitride decomposition condition

It is thus clear that nitric acid 5mL～10mL of adding ρ 1.42 is the abundant carbonization filter paper of ability all, adds 3mL～5mL perchloric acid again and can decompose boron nitride fully.In practical operation, add before the perchloric acid, the necessary abundant carbonization filter paper of low temperature is with blast protection.

7, coexistence elements interference experiment

Because therefore other constituent content does not seldom disturb the mensuration of boron in the mensuration system; But when facile hydrolysis elements such as containing niobium, tungsten in the solution exists, must do the filtration back and measure, be prone to stifled sampling system and measured value instability because of fine particle is arranged.

8, the detection limit of working curve, related coefficient, method

In 6 100mL plastics volumetric flasks; Pipetting concentration respectively is boron standard solution 0,1.00,2.50,5.00,10.00, the 20.00mL of 1.00 μ g/mL; The nitric acid 2mL of adding ρ 1.42g/mL, the perchloric acid 1mL of ρ 1.68g/mL are diluted with water to scale and shake up, and adopt icp ms to measure, and are internal standard element with the beryllium; The automatic drawing curve of instrument, its related coefficient is more than 0.999.

Result according to above-mentioned experiment obtains is applied to nitrogen in steel boron Determination on content method with the related parameter of confirming that has.The technical scheme that realizes this method is such, takes by weighing 1.0000g～2.0000g sample and places the 150mL quartz beaker, adds 20mL water, hydrochloric acid 8mL～12mL of ρ 1.19, nitric acid 8mL～12mL of ρ 1.42; The heating for dissolving sample after the question response calmness, takes off; Glass sand core funnel suction filtration (or with being covered with the glass funnel filtration of quantitative filter paper at a slow speed) in the shop filter membrane with hot high-purity washing 8～10 times, washes the deposition on the filter membrane in (or with filter paper and deposition immigration) 150mL quartz beaker; Nitric acid 2mL～3mL (when filter paper is arranged, adding the abundant carbonization filter paper of the 5mL～10mL nitric acid) dissolution in low temperature that adds ρ 1.42, perchloric acid 2mL～4mL of adding ρ 1.67; Continue heating for dissolving up to emitting the white cigarette of perchloric acid, take off, add the nitric acid dissolve salt of 5mL (1+1) to the wet salt shape; Move into again in the 100mL volumetric flask, be diluted with water to scale, shake up, in company with the band reagent blank; Adopt icp ms to measure boron in the boron nitride, converse the content of nitrogen in steel boron.

The drafting of working curve

In 6 100mL plastics volumetric flasks; Pipetting concentration respectively is boron standard solution 0,1.00,2.50,5.00,10.00, the 20.00mL of 1.00 μ g/mL; Add the nitric acid 2mL of ρ 1.42g/mL, the perchloric acid 1mL of ρ 1.68g/mL, be diluted with water to scale and shake up, adopt icp ms to measure; With the beryllium is internal standard element, the automatic drawing curve of instrument.

Computing formula is:

W_{BN} % = \frac{10^{- 6} \times ({m - m}_{0})}{m} \times \frac{M_{BN}}{M_{B}} \times 100

W in the formula _BN-represent the massfraction of boron nitride, %;

The numerical value of boron quality in m-sample solution, μ g;

m ₀The numerical value of boron quality in the-blank solution, μ g;

The numerical value of m-test portion quality, g;

M _BNThe molal weight of-boron nitride, g.mol ^-1

M _BThe molal weight of-boron, g.mol ^-1

Outstanding advantage of the present invention is to have set up a kind of nitrogen in steel boron Determination on content method, has filled up the blank in nitrogen in steel boron content analysis field.

Four, embodiment:

Below in conjunction with embodiment the present invention is done further description.

Embodiment 1

Take by weighing 1.0000gBT100H steel appearance and place the 150mL quartz beaker, add 20mL water, the hydrochloric acid 8mL of ρ 1.19, the nitric acid 10mL of ρ 1.42, the heating for dissolving sample is after the question response calmness; Take off, filter in the 100mL volumetric flask,, the part that does not contain boron nitride deposition filter paper is torn off with hot high purity water washing precipitation 10 times; To precipitate again together with filter paper and move in the 150mL quartz beaker the abundant carbonization filter paper of nitric acid 5mL low-temperature heat of adding ρ 1.42, the perchloric acid 3mL of adding ρ 1.67; Heating for dissolving emits the white cigarette of perchloric acid to the wet salt shape, takes off, and adds the nitric acid dissolve salt of 5mL (1+1); Move in the 100mL volumetric flask, be diluted with water to scale, shake up, in company with the band reagent blank; Adopt the content of boron in the icp ms boron nitride, be converted into the content of nitrogen in steel boron again, measure the result and see table 6.

The drafting of working curve

Computing formula is:

W_{BN} % = \frac{10^{- 6} \times ({m - m}_{0})}{m} \times \frac{M_{BN}}{M_{B}} \times 100

W in the formula _BN-represent the massfraction of boron nitride, %;

The numerical value of boron quality in m-sample solution, μ g;

m ₀The numerical value of boron quality in the-blank solution, μ g;

The numerical value of m-test portion quality, g;

M _BNThe molal weight of-boron nitride, g.mol ^-1

M _BThe molal weight of-boron, g.mol ^-1

Embodiment 2

Take by weighing 1.0000gBT100H steel appearance and place the 150mL quartz beaker, add 20mL water, the hydrochloric acid 10mL of ρ 1.19, the nitric acid 10mL of ρ 1.42, the heating for dissolving sample is after the question response calmness; Take off, in the glass sand core funnel suction filtration of shop filter membrane, with hot high purity water washing precipitation 8 times; Deposition is washed in the 150mL quartz beaker, add the nitric acid 3mL of ρ 1.42, the perchloric acid 3mL of ρ 1.67, heating for dissolving emits the white cigarette of perchloric acid to the wet salt shape; Take off, add the nitric acid dissolve salt of 5mL (1+1), move in the 100mL volumetric flask; Be diluted with water to scale, shake up,, adopt icp ms to measure the content of boron in the boron nitride in company with the band reagent blank; Converse the content of nitrogen in steel boron again, computing formula is measured the result and is seen table 6 with embodiment 1.

The drafting of working curve

In 6 100mL plastics volumetric flasks; Pipetting concentration respectively is boron standard solution 0,1.00,2.50,5.00,10.00, the 20.00mL of 1.00 μ g/mL; The nitric acid 2mL of adding ρ 1.42g/mL, the perchloric acid 1mL of ρ 1.68g/mL are diluted with water to scale and shake up; The employing icp ms is measured, and is internal standard element with the beryllium, the automatic drawing curve of instrument.

Embodiment 3

Take by weighing 1.0000gQ690 steel appearance and place the 150mL quartz beaker, add 20mL water, the hydrochloric acid 10mL of ρ 1.19, the nitric acid 8mL of ρ 1.42, the heating for dissolving sample; After the question response calmness, take off, filter in the 100mL volumetric flask; With hot high purity water washing precipitation 10 times, the part that does not contain boron nitride deposition filter paper is torn off, will precipitate again together with in the filter paper immigration 150mL quartz beaker; The abundant carbonization filter paper of nitric acid 6mL low-temperature heat that adds ρ 1.42, the perchloric acid 3mL of adding ρ 1.67, heating for dissolving emits the white cigarette of perchloric acid to the wet salt shape; Take off, add the nitric acid dissolve salt of 5mL (1+1), move in the 100mL volumetric flask; Be diluted with water to scale, shake up,, adopt icp ms to measure boron in the boron nitride in company with the band reagent blank; Converse the content of nitrogen in steel boron, computing formula is measured the result and is seen table 6 with embodiment 1.

The drafting of working curve

Embodiment 4

Take by weighing 1.0000g3 ^#Steel appearance places the 150mL quartz beaker, adds 20mL water, the hydrochloric acid 8mL of ρ 1.19, the nitric acid 9mL of ρ 1.42, and the heating for dissolving sample is after the question response calmness; Take off, filter in the 100mL volumetric flask,, the part that does not contain boron nitride deposition filter paper is torn off with hot high purity water washing precipitation 10 times; To precipitate together with in the filter paper immigration 150mL quartz beaker again, and add the abundant carbonization filter paper of nitric acid 5mL low-temperature heat of ρ 1.42, and add the perchloric acid 3mL of ρ 1.67, heating for dissolving emits the white cigarette of perchloric acid to the wet salt shape; Take off, add the nitric acid dissolve salt of 4mL (1+1), move in the 100mL volumetric flask; Be diluted with water to scale, shake up,, adopt icp ms to measure boron in the boron nitride in company with the band reagent blank; Converse the content of nitrogen in steel boron, computing formula is with embodiment 1, and the result sees table 6.

The drafting of working curve

In 6 100mL plastics volumetric flasks; Pipetting concentration respectively is boron standard solution 0,1.00,2.50,5.00,10.00, the 20.00mL of 1.00 μ g/mL; The nitric acid 2mL of adding ρ 1.42g/mL, the perchloric acid 1mL of ρ 1.68g/mL are diluted with water to scale, shake up, and adopt icp ms to measure; With the beryllium is internal standard element, the automatic drawing curve of instrument.

Table 6: measure % as a result

Sample	Composition	Measured value	Composition	Measured value
					BT100H steel appearance	Boron in the boron nitride	0.00057	Boron nitride	0.0013
BT100H steel appearance	Boron in the boron nitride	0.00060	Boron nitride	0.0014
					Q690	Boron in the boron nitride	0.00029	Boron nitride	0.00067
3 ^#Steel appearance	Boron in the boron nitride	0.00031	Boron nitride	0.00071

Claims

, a kind of nitrogen in steel boron Determination on content method, it is characterized in that sample processes bits appearance, determination step is following:

1), taking by weighing 1.0000g～2.0000g sample places the 150mL quartz beaker, adding 20mL water, hydrochloric acid 8mL～12mL of ρ 1.19, nitric acid 8mL～12mL of ρ 1.42, heating for dissolving sample; After the question response calmness, take off, in the glass sand core funnel suction filtration (or with being covered with the glass funnel filtration of quantitative filter paper at a slow speed) of shop filter membrane; With hot high purity water washing precipitation 8～10 times, the deposition on the filter membrane is washed in (or with filter paper and deposition immigration) 150mL quartz beaker, the nitric acid 2mL～3mL that adds ρ 1.42 is (when having filter paper; Add the abundant carbonization filter paper of 5mL～10mL nitric acid) dissolution in low temperature, perchloric acid 2mL～4mL of adding ρ 1.67 continues heating for dissolving up to emitting the white cigarette of perchloric acid to the wet salt shape; Take off, add the nitric acid dissolve salt of 100mL (1+1), move in the 50mL volumetric flask; Be diluted with water to scale, shake up; In company with the band reagent blank, adopt icp ms to measure boron in the boron nitride, converse the content of nitrogen in steel boron;

2), the drafting of working curve

In 6 100mL plastics volumetric flasks; Pipetting concentration respectively is boron standard solution 0,1.00,2.50,5.00,10.00, the 20.00mL of 1.00 μ g/mL; The nitric acid 2mL of adding ρ 1.42g/mL, the perchloric acid 1mL of ρ 1.68g/mL are diluted with water to scale and shake up; The employing icp ms is measured, and is internal standard element with the beryllium, the automatic drawing curve of instrument;

Computing formula is: $W_{BN} % = \frac{10^{- 6} \times ({m - m}_{0})}{m} \times \frac{M_{BN}}{M_{B}} \times 100$

W in the formula _BN-represent the massfraction of boron nitride, %;

The numerical value of boron quality in m-sample solution, μ g;

m ₀The numerical value of boron quality in the-blank solution, μ g;

The numerical value of m-test portion quality, g;

M _BNThe molal weight of-boron nitride, g.mol ^-1

M _BThe molal weight of-boron, g.mol ^-1
2. nitrogen in steel boron Determination on content method according to claim 1 is characterized in that can quantitatively keeping boron nitride with the nitration mixture separation solid solution boron of nitric acid, hydrochloric acid and the boride of other form, decomposes boron nitride with nitric acid, perchloric acid.