CN104215738A - Method for simultaneously determining Zr, Cu and Ni contents in Zr-Cu-Ni-Al amorphous alloy - Google Patents

Abstract

The invention provides a method for simultaneously determining Zr, Cu and Ni contents in Zr-Cu-Ni-Al amorphous alloy. The Zr, Cu and Ni are determined by using EDTA complexing back titration, the Zr, Cu, Ni and Al can be directly determined by using back titration in an acidic medium without interference according to a complexing stability constant; the Cu content and Ni content are determined by using the F- to shelter the Zr and Al under the acidity of pH 5-6, and the Ni content is determined by using thiorea to shelter the Cu, and the content of the Cu is obtained according to a computational formula. The contents of the Zr, Cu and Ni are determined in parallel through once sample preparation. The operation is free from electrolysis equipment, according to acidity ranges for EDTA complexing titration of different elements, the F- is used for sheltering the Zr and Al, and the thiorea is used for sheltering the Cu, so that the interference among the elements is eliminated, the titration end point sensitivity and the result accuracy are improved by using the back titration, and the content values of Zr, Cu and Ni can be fast and stably obtained.

Description

A kind of method of Zr, Cu, Ni content in simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal

Technical field

The invention belongs to chemical analysis technology field, relate to the method for Zr, Cu, Ni content in a kind of simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal.

Background technology

At present, the joint measurement method of Zr, Cu, Ni content in Zr-Cu-Ni-Al non-crystaline amorphous metal is not all had in GB and navigation mark." chemical analysis metering " 1999 04 interim to be inquired the simultaneous determination of copper, zirconium content " in the copper zirconium intermediate alloy ", and copper electrolytic process carries out gravimetric determination after being separated, and the solution after separating copper directly carries out the titration of EDTA volumetric method.Copper detachment process is complicated in the above-mentioned methods, and needs electrolysis special equipment, is not also suitable for the mensuration of nickel-containing material.In conventional analysis, high-load zirconium, nickel adopt precipitate and separate, and result is accurate, reliable, but determination period is long, complex operation, adopts titrimetry in general work more, conventional direct titrimetric method or back titration.Very easily generate multinuclear hydroxyl compound in direct titration, must heat before titration and boil, titration while hot, and terminal repeatedly, Lower result.And zirconium is measured for back titration, because operation control overflow is inadequate in existing document, measurement result error is also large; The complexing stability constant of Cu, Ni, Al and EDTA is close, mutually disturbs under Coexistence Situation in titration process, cannot directly measure.

Through update search do not find special for Zr-Cu-Ni-Al non-crystaline amorphous metal in the simultaneous determination technical patent of Zr, Cu, Ni and report.

Summary of the invention

The object of the invention is to provide that a kind of running time is short, and process is simple, titration end-point sudden change obviously, and the simultaneous determination technology of Zr, Cu, Ni in the Zr-Cu-Ni-Al non-crystaline amorphous metal that the recovery is high, precision is good.

Technical scheme of the present invention is:

The method of Zr, Cu, Ni content in described a kind of simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal, is characterized in that: comprise the following steps:

Step 1:Zr-Cu-Ni-Al non-crystaline amorphous metal sample weighs: accurately take Zr-Cu-Ni-Al non-crystaline amorphous metal sample;

Step 2:Zr-Cu-Ni-Al non-crystaline amorphous metal sample dissolves smolders: in the beaker holding Zr-Cu-Ni-Al non-crystaline amorphous metal sample, add sulfuric acid and 2g solid ammonium sulfate that 10mL density is 1.84g/mL successively, beaker is placed in electric furnace to be heated to beaker solution limpid, continue to be heated to solution and emit white cigarette, add the nitric acid that 2mL density is 1.42g/mL again, continue heating beaker to solution and emit white cigarette, beaker is taken off from electric furnace, naturally cool to room temperature, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering;

Step 3:Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution constant volume: the wall of cup holding the beaker of the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering with distilled water purge, solution in beaker is transferred in the volumetric flask of SmL, with distilled water diluting to scale, shake up, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution A that constant volume is SmL;

The titration of Zr, Ni, Cu in step 4:Zr-Cu-Ni-Al non-crystaline amorphous metal:

1) divide and to get in step 3 solution A 0.2SmL in the first conical flask, the hydrochloric acid that 5mL density is 1.19g/mL is added in the first conical flask, in this solution, EDTA standard solution is added again after shaking up, the a small amount of water of conical flask wall is rinsed, shake up 15 seconds, add boiling water and 2 xylenol orange indicator, be titrated to purple with basic zirconium chloride standard solution, calculate the content of Zr:

$\mathrm{Zr}\%=\frac{5(C_1{V}_1-C_2{V}_2)\×91.224}{M}\×100\%$

Wherein C ₁for the concentration of this step e DTA standard solution, V ₁for the volume of the EDTA standard solution that this step adds, C ₂for this step basic zirconium chloride concentration of standard solution, V ₂for the volume of the basic zirconium chloride standard solution that this step adds, M is the sample weighting amount of Zr-Cu-Ni-Al non-crystaline amorphous metal sample;

2) divide and to get in step 3 solution A 0.2SmL in the second conical flask, the solid fluorinated sodium of 2g and 2g solid thiocarbamide is added successively in the second conical flask, with distilled water purge second conical flask wall, after shaking up, EDTA standard solution and 2 0.2% p-nitrophenol indicator are added successively again in this solution, after shaking up, in solution, drip Ammonia to solution is micro-yellow, then adds 20mL acetic acid-ammonium acetate buffer solution and 2 xylenol orange indicator successively; Be titrated to purple with Zinc standard solution again, calculate the content of Ni:

$\mathrm{Ni}\%=\frac{5(C_3{V}_3-C_4{V}_4)\×58.693}{M}\×100\%$

Wherein C ₃for the concentration of this step e DTA standard solution, V ₃for the volume of the EDTA standard solution that this step adds, C ₄for this step Zinc standard solution concentration, V ₄for the volume of the Zinc standard solution that this step adds;

3) divide and to get in step 3 solution A 0.2SmL in triconic bottle, the solid fluorinated sodium of 2g is added in triconic bottle, with distilled water purge triconic bottle bottle wall, after shaking up, EDTA standard solution and 2 0.2% p-nitrophenol indicator are added successively again in this solution, after shaking up, in solution, drip Ammonia to solution is micro-yellow, add 20mL acetic acid-ammonium acetate buffer solution and 2 xylenol orange indicator more successively, be titrated to purple with Zinc standard solution again, calculate the content of Cu:

$\mathrm{Cu}\%=\frac{5(C_5{V}_5-C_6{V}_6)\×63.546}{M}-\mathrm{Ni}\%\×\frac{63.546}{58.693}$

Wherein C ₅for the concentration of this step e DTA standard solution, V ₅for the volume of the EDTA standard solution that this step adds, C ₆for this step Zinc standard solution concentration, V ₆for the volume of the Zinc standard solution that this step adds.

Further pre-program, the method of Zr, Cu, Ni content in described a kind of simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal, it is characterized in that: the pH value of acetic acid-ammonium acetate buffer solution is 5.5, be dissolved in 300mL water by taking sodium acetate 80g, add glacial acetic acid 10mL again, shake up after being diluted to 1L and obtain.

Further pre-program, the method of Zr, Cu, Ni content in described a kind of simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal, it is characterized in that: EDTA standard solution is dissolved in 500mL water by taking 7.45gEDTA, then moves in 1000mL volumetric flask, shakes up and obtain after being diluted with water to scale.

Further pre-program, the method of Zr, Cu, Ni content in described a kind of simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal, it is characterized in that: basic zirconium chloride standard solution is by taking 3.2225g basic zirconium chloride, keep micro-boil 5 minutes with the 100mL hydrochloric acid solution heating for dissolving basic zirconium chloride of 3.6mol/L, proceed to after cooling in 1000mL volumetric flask, shake up after being diluted with water to scale and obtain.

Further pre-program, the method of Zr, Cu, Ni content in described a kind of simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal, it is characterized in that: Zinc standard solution is by being cut into grain of rice shape by zinc granule, rinse rapidly with the hydrochloric acid of 1+1, then wash three times, after oven dry with alcohol, weigh 0.6537 gram, add the hydrochloric acid 10mL of 1+1 again, the zinc granule that dissolution in low temperature obtains after weighing, after cooling, constant volume obtains in 1000mL volumetric flask.

Beneficial effect

Square ratio juris in the present invention:

In the present invention, Zr, Cu, Ni all adopt EDTA Complexometric B ack-Titration method, and according to complexing stability constant, in acid medium, directly measure Zr by the method for back titration, Cu, Ni, Al do not disturb; F is used under the acidity of PH5-6 ^-shelter Zr, Al, measure Cu, Ni resultant, then shelter Cu with thiocarbamide, measure Ni content, obtain the content of Cu according to computing formula.Zr, Cu, Ni, Al and EDTA, thiocarbamide, F is listed in table 1 ^-complexing stability constant

Table 1

?

Cu 2+

Cu +

Zr 4+

Ni 2+

Al 3+

EDTA	18.8	/	29.5	18.62	16.11
						F -	1.23	/	35.40	0.66	19.84
Thiocarbamide	/	15.4	/	1.05	/

In sum, this method passes through a sample preparation, the content of replicate determination Zr, Cu, Ni.Operation does not need electrolysis installation, according to the Acidity Range of different element EDTA complexometry, selects F respectively ^-shelter Zr, Al, shelter the interference between Cu eliminating element with thiocarbamide, utilize back titration, improve titration end-point sensitivity and result precision, fast and stable obtains Zr, Cu, Ni content value.

The advantage of this method:

(1) this method is without the need to being separated, and without the need to electrolysis special equipment, once molten sample, directly carries out the content of EDTA volumetric method simultaneous titration Zr, Cu, Ni.

(2) when measuring Zr, control operation process, shakes up 15 seconds, makes Zr and EDTA complexing complete, utilizes back titration, avoid the hydrolysising loss of Zr, records result accurate, stable.

(3) for the situation that Zr-Cu-Ni-Al coexists, select suitable screening agent and suitable titratable acidity, terminal is obvious, stable, and by calculating, obtains the value of Zr, Cu, Ni respectively.

(4) this method is fast and simple, and use reagent simple, conventional, analytical cycle is short.

(5) this method is not only applicable to Zr-Cu-Ni-Al, same is suitable for and the series material constituent analysis such as Zr-Cu, Zr-Cu-Ni, Zr-Ni, pure Zr.

Embodiment

Embodiment 1:

The present embodiment is the method for Zr, Cu, Ni content in a kind of simultaneous determination Zr55Cu30Al10Ni5.

Step 1:Zr-Cu-Ni-Al non-crystaline amorphous metal sample weighs: take 0.2994gZr-Cu-Ni-Al non-crystaline amorphous metal sample, be accurate to 0.0001g, be placed in the beaker of 250mL.Obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample of precise.

Step 2:Zr-Cu-Ni-Al non-crystaline amorphous metal sample dissolves smolders: in the beaker of Zr-Cu-Ni-Al non-crystaline amorphous metal sample holding precise, add the sulfuric acid and 2g solid ammonium sulfate that 10mL density is 1.84g/mL successively, beaker is placed in electric furnace to be heated to beaker solution limpid, continue to be heated to solution and emit white cigarette, add the nitric acid that 2mL density is 1.42g/mL again, continue heating beaker to solution and emit white cigarette, beaker is taken off from electric furnace, naturally cool to room temperature, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering.

Step 3:Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution constant volume: the wall of cup holding the beaker of the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering with distilled water purge, solution in beaker is transferred in the volumetric flask of 100mL, with distilled water diluting to scale, shake up, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution A that constant volume is 100mL.

The titration of Zr, Ni, Cu in step 4:Zr-Cu-Ni-Al non-crystaline amorphous metal:

1) divide that to get solution A 20mL in step 3 be in first conical flask of 500mL to volume, the hydrochloric acid that 5mL density is 1.19g/mL is added in the first conical flask, in this solution, add the EDTA standard solution of 19.00mL0.02mol/L after shaking up again, the Zr that the volume ratio of the EDTA standard solution added here calculates consumes the amount of EDTA little over amount about 1 ~ 2ml.The a small amount of water of first conical flask wall is rinsed, shakes up 15 seconds, add 100mL boiling water and 2 0.25% xylenol orange indicator, be titrated to purple with 0.01mol/L basic zirconium chloride standard solution, calculate the content of Zr:

$\mathrm{Zr}\%=\frac{5(C_1{V}_1-C_2{V}_2)\×91.224}{M}\×100\%$

Wherein C ₁for actual actual concentrations 0.01999mol/L, the V of this step e DTA standard solution ₁for the volume 19.00mL of the EDTA standard solution that this step adds, C ₂for actual actual concentrations 0.01004mol/L, the V of this step basic zirconium chloride standard solution ₂for the volume 1.91mL of the basic zirconium chloride standard solution that this step adds, M are the sample weighting amount 0.2994g of Zr-Cu-Ni-Al non-crystaline amorphous metal sample; Zr%=54.94% is obtained according to formulae discovery.

2) divide that to get solution A 20mL in step 3 be in second conical flask of 500mL to volume, the solid fluorinated sodium of 2g and 2g solid thiocarbamide is added successively in the second conical flask, with distilled water purge second conical flask wall, after shaking up, then in this solution, add EDTA standard solution and 2 0.2% p-nitrophenol indicator of 4.00mL 0.02mol/L successively.The amount of the EDTA of the Ni consumption of the volume ratio calculating of the EDTA standard solution added here is little over amount 1 ~ 2mL.After shaking up, in solution, dripping Ammonia to solution with dropper is micro-yellow, then adds 20mL acetic acid-ammonium acetate buffer solution and 2 xylenol orange indicator successively; Be titrated to purple with the Zinc standard solution of 0.01mol/L again, calculate the content of Ni:

$\mathrm{Ni}\%=\frac{5(C_3{V}_3-C_4{V}_4)\×58.693}{M}\×100\%$

Wherein C ₃for actual actual concentrations 0.01999mol/L, the V of this step e DTA standard solution ₃for the volume 4.00mL of the EDTA standard solution that this step adds, C ₄for actual actual concentrations 0.01006mol/L, the V of this step Zinc standard solution ₄for the volume 2.52mL of the Zinc standard solution that this step adds; Ni%=5.35% is obtained according to formulae discovery.

3) divide that to get solution A 20mL in step 3 be in the triconic bottle of 500mL to volume, the solid fluorinated sodium of 2g is added in triconic bottle, with distilled water purge triconic bottle bottle wall, after shaking up, then in this solution, add EDTA standard solution and 2 0.2% p-nitrophenol indicator of 18.00mL 0.02mol/L successively.The resultant of the EDTA of Ni and the Cu consumption of the volume ratio calculating of the EDTA standard solution added here is little over amount 1 ~ 2mL.After shaking up, in solution, dripping Ammonia to solution with dropper is micro-yellow, add 20mL acetic acid-ammonium acetate buffer solution and 2 0.25% xylenol orange indicator more successively, then be titrated to purple with the Zinc standard solution of 0.01mol/L, calculate the content of Cu:

$\mathrm{Cu}\%=\frac{5(C_5{V}_5-C_6{V}_6)\×63.546}{M}-\mathrm{Ni}\%\×\frac{63.546}{58.693}$

Wherein C ₅for actual actual concentrations 0.01999mol/L, the V of this step e DTA standard solution ₅for the volume 18.00mL of the EDTA standard solution that this step adds, C ₆for actual actual concentrations 0.01006mol/L, the V of this step Zinc standard solution ₆for the volume 2.50mL of the Zinc standard solution that this step adds, obtain Cu%=29.72% according to formulae discovery.

In the present embodiment, the reagent of employing is obtained by following process:

The pH value of acetic acid-ammonium acetate buffer solution is 5.5, being dissolved in 300mL water, then adding glacial acetic acid 10mL, shaking up and obtaining after being diluted to 1L by taking sodium acetate 80g.

EDTA standard solution is dissolved in 500mL water by taking 7.45gEDTA, then moves in 1000mL volumetric flask, shakes up and obtain after being diluted with water to scale.

Basic zirconium chloride standard solution, by taking 3.2225g basic zirconium chloride, keeps micro-boil 5 minutes with the 100mL hydrochloric acid solution heating for dissolving basic zirconium chloride of 3.6mol/L, proceed in 1000mL volumetric flask, shake up and obtain after being diluted with water to scale after cooling.

Zinc standard solution, by zinc granule is cut into grain of rice shape, rinses rapidly with the hydrochloric acid of 1+1, then washes three times with alcohol, after oven dry, weigh 0.6537 gram, then add the hydrochloric acid 10mL of 1+1, the zinc granule that dissolution in low temperature obtains after weighing, after cooling, constant volume obtains in 1000mL volumetric flask.

Embodiment 2:

The present embodiment is the method for Zr, Cu, Ni content in a kind of simultaneous determination Zr67Cu26Al4Ni3.

Step 1:Zr-Cu-Ni-Al non-crystaline amorphous metal sample weighs: take 0.3002g Zr-Cu-Ni-Al non-crystaline amorphous metal sample, be accurate to 0.0001g, be placed in the beaker of 250mL.Obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample of precise.

Step 2:Zr-Cu-Ni-Al non-crystaline amorphous metal sample dissolves smolders: in the beaker of Zr-Cu-Ni-Al non-crystaline amorphous metal sample holding precise, add the sulfuric acid and 2g solid ammonium sulfate that 10mL density is 1.84g/mL successively, beaker is placed in electric furnace to be heated to beaker solution limpid, continue to be heated to solution and emit white cigarette, add the nitric acid that 2mL density is 1.42g/mL again, continue heating beaker to solution and emit white cigarette, beaker is taken off from electric furnace, naturally cool to room temperature, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering.

Step 3:Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution constant volume: the wall of cup holding the beaker of the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering with distilled water purge, solution in beaker is transferred in the volumetric flask of 100mL, with distilled water diluting to scale, shake up, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution A that constant volume is 100mL.

The titration of Zr, Ni, Cu in step 4:Zr-Cu-Ni-Al non-crystaline amorphous metal:

1) divide that to get solution A 20mL in step 3 be in first conical flask of 500mL to volume, the hydrochloric acid that 5mL density is 1.19g/mL is added in the first conical flask, in this solution, add the EDTA standard solution of 23.00mL0.02mol/L after shaking up again, the Zr that the volume ratio of the EDTA standard solution added here calculates consumes the amount of EDTA little over amount about 1 ~ 2ml.The a small amount of water of first conical flask wall is rinsed, shakes up 15 seconds, add 100mL boiling water and 2 0.25% xylenol orange indicator, be titrated to purple with 0.01mol/L basic zirconium chloride standard solution, calculate the content of Zr:

$\mathrm{Zr}\%=\frac{5(C_1{V}_1-C_2{V}_2)\×91.224}{M}\×100\%$

Wherein C ₁for actual actual concentrations 0.01999mol/L, the V of this step e DTA standard solution ₁for the volume 23.00mL of the EDTA standard solution that this step adds, C ₂for actual actual concentrations 0.01004mol/L, the V of this step basic zirconium chloride standard solution ₂for the volume 1.75mL of the basic zirconium chloride standard solution that this step adds, M are the sample weighting amount 0.3002g of Zr-Cu-Ni-Al non-crystaline amorphous metal sample; Zr%=67.18% is obtained according to formulae discovery.

2) divide that to get solution A 20mL in step 3 be in second conical flask of 500mL to volume, the solid fluorinated sodium of 2g and 2g solid thiocarbamide is added successively in the second conical flask, with distilled water purge second conical flask wall, after shaking up, then in this solution, add EDTA standard solution and 2 0.2% p-nitrophenol indicator of 3.00mL 0.02mol/L successively.The amount of the EDTA of the Ni consumption of the volume ratio calculating of the EDTA standard solution added here is little over amount 1 ~ 2mL.After shaking up, in solution, dripping Ammonia to solution with dropper is micro-yellow, then adds 20mL acetic acid-ammonium acetate buffer solution and 2 xylenol orange indicator successively; Be titrated to purple with the Zinc standard solution of 0.01mol/L again, calculate the content of Ni:

$\mathrm{Ni}\%=\frac{5(C_3{V}_3-C_4{V}_4)\×58.693}{M}\×100\%$

Wherein C ₃for actual actual concentrations 0.01999mol/L, the V of this step e DTA standard solution ₃for the volume 3.00mL of the EDTA standard solution that this step adds, C ₄for actual actual concentrations 0.01006mol/L, the V of this step Zinc standard solution ₄for the volume 2.82mL of the Zinc standard solution that this step adds; Ni%=3.09% is obtained according to formulae discovery.

3) divide that to get solution A 20mL in step 3 be in the triconic bottle of 500mL to volume, the solid fluorinated sodium of 2g is added in triconic bottle, with distilled water purge triconic bottle bottle wall, after shaking up, then in this solution, add EDTA standard solution and 2 0.2% p-nitrophenol indicator of 15.00mL 0.02mol/L successively.The resultant of the EDTA of Ni and the Cu consumption of the volume ratio calculating of the EDTA standard solution added here is little over amount 1 ~ 2mL.After shaking up, in solution, dripping Ammonia to solution with dropper is micro-yellow, add 20mL acetic acid-ammonium acetate buffer solution and 2 0.25% xylenol orange indicator more successively, then be titrated to purple with the Zinc standard solution of 0.01mol/L, calculate the content of Cu:

$\mathrm{Cu}\%=\frac{5(C_5{V}_5-C_6{V}_6)\×63.546}{M}-\mathrm{Ni}\%\×\frac{63.546}{58.693}$

Wherein C ₅for actual actual concentrations 0.01999mol/L, the V of this step e DTA standard solution ₅for the volume 15.00mL of the EDTA standard solution that this step adds, C ₆for actual actual concentrations 0.01006mol/L, the V of this step Zinc standard solution ₆for the volume 2.40mL of the Zinc standard solution that this step adds, obtain Cu%=25.84% according to formulae discovery.

In the present embodiment, the reagent of employing is obtained by following process:

The pH value of acetic acid-ammonium acetate buffer solution is 5.5, being dissolved in 300mL water, then adding glacial acetic acid 10mL, shaking up and obtaining after being diluted to 1L by taking sodium acetate 80g.

EDTA standard solution is dissolved in 500mL water by taking 7.45gEDTA, then moves in 1000mL volumetric flask, shakes up and obtain after being diluted with water to scale.

Basic zirconium chloride standard solution, by taking 3.2225g basic zirconium chloride, keeps micro-boil 5 minutes with the 100mL hydrochloric acid solution heating for dissolving basic zirconium chloride of 3.6mol/L, proceed in 1000mL volumetric flask, shake up and obtain after being diluted with water to scale after cooling.

Zinc standard solution, by zinc granule is cut into grain of rice shape, rinses rapidly with the hydrochloric acid of 1+1, then washes three times with alcohol, after oven dry, weigh 0.6537 gram, then add the hydrochloric acid 10mL of 1+1, the zinc granule that dissolution in low temperature obtains after weighing, after cooling, constant volume obtains in 1000mL volumetric flask.

Claims (5)

1. the method for Zr, Cu, Ni content in simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal, is characterized in that: bag

Draw together following steps:

Step 1:Zr-Cu-Ni-Al non-crystaline amorphous metal sample weighs: accurately take Zr-Cu-Ni-Al non-crystaline amorphous metal sample;

Step 2:Zr-Cu-Ni-Al non-crystaline amorphous metal sample dissolves smolders: in the beaker holding Zr-Cu-Ni-Al non-crystaline amorphous metal sample, add sulfuric acid and 2g solid ammonium sulfate that 10mL density is 1.84g/mL successively, beaker is placed in electric furnace to be heated to beaker solution limpid, continue to be heated to solution and emit white cigarette, add the nitric acid that 2mL density is 1.42g/mL again, continue heating beaker to solution and emit white cigarette, beaker is taken off from electric furnace, naturally cool to room temperature, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering;

Step 3:Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution constant volume: the wall of cup holding the beaker of the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution after smoldering with distilled water purge, solution in beaker is transferred in the volumetric flask of SmL, with distilled water diluting to scale, shake up, obtain the Zr-Cu-Ni-Al non-crystaline amorphous metal sample solution A that constant volume is SmL;

The titration of Zr, Ni, Cu in step 4:Zr-Cu-Ni-Al non-crystaline amorphous metal:

1) divide and to get in step 3 solution A 0.2SmL in the first conical flask, the hydrochloric acid that 5mL density is 1.19g/mL is added in the first conical flask, in this solution, EDTA standard solution is added again after shaking up, the a small amount of water of conical flask wall is rinsed, shake up 15 seconds, add boiling water and 2 xylenol orange indicator, be titrated to purple with basic zirconium chloride standard solution, calculate the content of Zr:

$\mathrm{Zr}\%=\frac{5(C_1{V}_1-C_2{V}_2)\×91.224}{M}\×100\%$

Wherein C ₁for the concentration of this step e DTA standard solution, V ₁for the volume of the EDTA standard solution that this step adds, C ₂for this step basic zirconium chloride concentration of standard solution, V ₂for the volume of the basic zirconium chloride standard solution that this step adds, M is the sample weighting amount of Zr-Cu-Ni-Al non-crystaline amorphous metal sample;

2) divide and to get in step 3 solution A 0.2SmL in the second conical flask, the solid fluorinated sodium of 2g and 2g solid thiocarbamide is added successively in the second conical flask, with distilled water purge second conical flask wall, after shaking up, EDTA standard solution and 2 0.2% p-nitrophenol indicator are added successively again in this solution, after shaking up, in solution, drip Ammonia to solution is micro-yellow, then adds 20mL acetic acid-ammonium acetate buffer solution and 2 xylenol orange indicator successively; Be titrated to purple with Zinc standard solution again, calculate the content of Ni:

$\mathrm{Ni}\%=\frac{5(C_3{V}_3-C_4{V}_4)\×58.693}{M}\×100\%$

Wherein C ₃for the concentration of this step e DTA standard solution, V ₃for the volume of the EDTA standard solution that this step adds, C ₄for this step Zinc standard solution concentration, V ₄for the volume of the Zinc standard solution that this step adds;

3) divide and to get in step 3 solution A 0.2SmL in triconic bottle, the solid fluorinated sodium of 2g is added in triconic bottle, with distilled water purge triconic bottle bottle wall, after shaking up, EDTA standard solution and 2 0.2% p-nitrophenol indicator are added successively again in this solution, after shaking up, in solution, drip Ammonia to solution is micro-yellow, add 20mL acetic acid-ammonium acetate buffer solution and 2 xylenol orange indicator more successively, be titrated to purple with Zinc standard solution again, calculate the content of Cu:

$\mathrm{Cu}\%=\frac{5(C_5{V}_5-C_6{V}_6)\×63.546}{M}-\mathrm{Ni}\%\×\frac{63.546}{58.693}$

Wherein C ₅for the concentration of this step e DTA standard solution, V ₅for the volume of the EDTA standard solution that this step adds, C ₆for this step Zinc standard solution concentration, V ₆for the volume of the Zinc standard solution that this step adds.

2. a kind of method of Zr, Cu, Ni content in simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal according to claim 1, it is characterized in that: the pH value of acetic acid-ammonium acetate buffer solution is 5.5, be dissolved in 300mL water by taking sodium acetate 80g, add glacial acetic acid 10mL again, shake up after being diluted to 1L and obtain.

3. a kind of method of Zr, Cu, Ni content in simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal according to claim 1, it is characterized in that: EDTA standard solution is dissolved in 500mL water by taking 7.45gEDTA, move into again in 1000mL volumetric flask, shake up after being diluted with water to scale and obtain.

4. a kind of method of Zr, Cu, Ni content in simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal according to claim 1, it is characterized in that: basic zirconium chloride standard solution is by taking 3.2225g basic zirconium chloride, keep micro-boil 5 minutes with the 100mL hydrochloric acid solution heating for dissolving basic zirconium chloride of 3.6mol/L, proceed to after cooling in 1000mL volumetric flask, shake up after being diluted with water to scale and obtain.

5. a kind of method of Zr, Cu, Ni content in simultaneous determination Zr-Cu-Ni-Al non-crystaline amorphous metal according to claim 1, it is characterized in that: Zinc standard solution is by being cut into grain of rice shape by zinc granule, rinse rapidly with the hydrochloric acid of 1+1, three times are washed again with alcohol, after oven dry, weigh 0.6537 gram, then add the hydrochloric acid 10mL of 1+1, the zinc granule that dissolution in low temperature obtains after weighing, after cooling, constant volume obtains in 1000mL volumetric flask.