CN104730201A - Measurement method for content of hydrofluoric acid in titanium alloy pickling solution - Google Patents
Measurement method for content of hydrofluoric acid in titanium alloy pickling solution Download PDFInfo
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Abstract
The invention discloses a measurement method for content of hydrofluoric acid in a titanium alloy pickling solution. The titanium alloy pickling solution comprises the main components including nitric acid, the hydrofluoric acid and fluorotitanic acid. The measurement method adopts an acid-base titration method for measuring the content of the fluorotitanic acid, and adopts a calcium fluoride precipitation method for measuring the content of total fluorine in a bath solution; and the content of the fluorine in the fluorotitanic acid is subtracted by the content of the total fluorine to obtain the content of the hydrofluoric acid in the solution. The measurement method has the advantages that the interferences caused by the fluorotitanic acid can be effectively avoided; the adding standard recovery rate of the content of the hydrofluoric acid, measured by adopting the method, is more than 95%; and the determination requirements on the concentration of the hydrofluoric acid are met and the production can be smoothly carried out.
Description
Technical field
The present invention relates to a kind of analytical approach of solution, be specifically related to the measuring method of fluohydric acid content in a kind of titanium alloy pickle.
Background technology
Titanium alloy is because having excellent corrosion-resistant, high specific strength, high tenacity and the performance characteristics such as can welding, important application is had in aeromotor field, the titanium alloy consumption of some advanced aero engines has accounted for 25 ~ 40% of engine weight, this just has higher requirement to the quality of titanium alloy parts, and its quality testing means are mainly fluorescent penetrant detection.
It is one of important method checking industrial component surface integrality that fluorescent penetrant detects.The fluorescent penetrant of titanium alloy parts detects, and be the flaws being detected surface of the work by the optical characteristics of some fluorescent material when Ultraviolet radiation, this method fast, accurately.Make a general survey of domestic and international advanced engine component detection technique, the parts of engine more than 90% need to carry out penetrating inspection, and this detection method has become the gordian technique ensureing end product quality.
The main technological steps that titanium alloy carries out fluorescent penetrant detection comprises: oil removing, washing, pickling, drying, infiltration, emulsification, washing, drying, video picture, drying, observation, washing etc., wherein, pickling is most important step before fluorescent penetrant detects, and the content of hydrofluorite directly affects the surface quality of titanium alloy in pickle, therefore, rapid and accurate determination fluohydric acid content, to the quality and the efficiency that improve current titanium alloy cleanup acid treatment, has important practical significance.Meanwhile, hydrofluorite detection technique is the key point of the further investigation of titanium alloy acid cleaning process and mechanism thereof efficiently.
At present, corporate boss will adopt thorium nitrate titration to survey fluohydric acid content, and this method, with alizarin red S indicator, cushions test solution pH with chloroacetic acid.For newly joining tank liquor, this method is comparatively accurate, and recovery of standard addition is 97 ~ 100%, and to longer tank liquor service time, due to the interference of impurity in tank liquor, the recovery of this method only has 85% ~ 90%.In addition, the titration end-point of this method is difficult to judge (gradual change and not mutated), and therefore this method is difficult to instruct actual production.
Summary of the invention
The invention provides the measuring method of fluohydric acid content in a kind of titanium alloy pickle, the method can meet the needs of actual production, the feature that favorable reproducibility, accuracy are high and practical.
The present invention is achieved like this, the measuring method of fluohydric acid content in a kind of titanium alloy pickle, the method of acid base titration is first adopted to measure the content of fluotitanic acid, calcium chloride precipitation method is adopted to measure total Oil repellent again, then deduct the Oil repellent in fluotitanic acid according to total fluoro quantity, just can calculate the content obtaining hydrofluorite in solution.
(1) determination of acid-basetitration fluotitanic acid content, accurately pipette titanium alloy pickle 5 ml in 100 ml plastics volumetric flasks, be diluted with water to scale, shake up, 5 ml are pipetted in 250 ml conical flasks in above-mentioned dilution, 10 ~ 20ml saturated potassium chloride solution is added, 15 ~ 30 ml absolute ethyl alcohols in conical flask; In above-mentioned test solution, add 1 ~ 2 phenolphthalein indicator again, dripping 0.1039 mol/L NaOH standard solution pink to test solution change is terminal; Above-mentioned test solution is heated to firm boiling, and continuing dropping 0.1039 mol/L NaOH standard solution pink to test solution change is terminal, record consumption V
1.
(2) calcium chloride precipitation method measures total Oil repellent, again pipettes titanium alloy pickle 5 ml in 100 ml plastics volumetric flasks, is diluted with water to scale, shakes up, pipette 5 ml in above-mentioned dilution in 250ml beaker, and add 10 ~ 20 ml deionized waters; In beaker, drip 2 mol/L NaOH solution 3 ~ 5 ml, be heated to firm boiling, flowing water-cooled; All be transferred in suction funnel by cooled test solution, miillpore filter suction filtration obtains filtrate.
Gained filtrate is all transferred in 500 ml conical flasks, adds 1 ~ 2 methyl red indicator, first drip 6 mol/L hydrochloric acid micro-red to solution, then drip 0.1039 mol/L NaOH standard solution and just turn yellow as terminal to test solution.
In above-mentioned test solution, accurately add 20 ml lime chloride standard solution, 5 min are boiled in heating, and after air cooling to room temperature, miillpore filter suction filtration obtains filtrate.Filtrate is all transferred in 250 ml conical flasks, 2mol/L NaOH solution is added in above-mentioned test solution, the 2 mol/L NaOH solution of 1.25 ml are added in every 10 ml test solutions, and add solid calcium indicator 0.05 g, dropping to solution with EDTA titrand, to become pure blue from claret be terminal, and record its consumption V
3.Parallel laboratory test three times, does blank assay simultaneously.
(3) deduct the Oil repellent in the fluotitanic acid content of measurement with the total Oil repellent measured, obtain the fluohydric acid content in titanium alloy pickle, its concrete formula is as follows: fluohydric acid content is calculated as follows:
（1）
In formula: C
hF---the concentration of hydrofluorite in titanium alloy pickle, g/L;
C
1---the concentration of NaOH titrand, mol/L;
V
1---the volume of the standard solution of sodium hydroxide consumed, ml;
C
2---the concentration of lime chloride titrand, mol/L;
V
2---the volume of the lime chloride titrand quantitatively added, ml;
C
3---the concentration of EDTA titrand, mol/L;
V
3---the volume of the EDTA standard solution consumed, ml;
V
0---get the volume of tank liquor, ml;
20.01---the relative molar mass of HF, g/mol.
Advantage of the present invention is: (1) this analysis method adopts " calcium fluoride precipitate+acid base titration " to test the content of hydrofluorite in pickle, and recovery of standard addition reaches height, can reach 95% ~ 105%; (2) this analytical approach is accurate and effective, cost is low, and enterprise produces and easily grasps; (3) this analytical approach can be analyzed the fluohydric acid content in titanium alloy pickle in commercial production and safeguard.
Embodiment
For the accuracy of check analysis method, carry out recovery of standard addition test to certain 4 dynamic pickle of the unknown, mark-on thing is hydrofluorite, mark-on 3 concentration levels.Specific implementation method is as follows:
Former state: get dynamic pickle 50 ml in 100ml plastics volumetric flask, be diluted with water to scale mark, shake up.
Add standard specimen 1: get dynamic pickle 50 ml in 100ml plastics volumetric flask, add the hydrofluorite 20ml that concentration is 8.650mol/L, be diluted with water to scale mark, shake up.
Add standard specimen 2: get dynamic pickle 50 ml in 100ml plastics volumetric flask, add the hydrofluorite 25ml that concentration is 8.650mol/L, be diluted with water to scale mark, shake up.
Add standard specimen 3: get dynamic pickle 50 ml in 100ml plastics volumetric flask, add the hydrofluorite 30ml that concentration is 8.650mol/L, be diluted with water to scale mark, shake up.
Then according to aforesaid analytical approach, above-mentioned sample is analyzed according to identical operation steps, acquired results in table 1, table 2, table 3, table 4.
The recovery of standard addition experimental result of the dynamic tank liquor 1 of table 1
The recovery of standard addition experimental result of the dynamic tank liquor 2 of table 2
The recovery of standard addition experimental result of the dynamic tank liquor 3 of table 3
The recovery of standard addition experimental result of the dynamic tank liquor 4 of table 4
From above-mentioned analysis result, the recovery of standard addition of analytical approach of the present invention reaches the requirement (95% ~ 105%) that enterprise specifies, meets production requirement.
Claims (5)
1. the measuring method of fluohydric acid content in a titanium alloy pickle, it is characterized in that: first adopt the method for acid base titration to measure the content of fluotitanic acid, calcium chloride precipitation method is adopted to measure total Oil repellent again, then deduct the Oil repellent in fluotitanic acid according to total fluoro quantity, just can calculate the content obtaining hydrofluorite in solution.
2. the measuring method of fluohydric acid content in a kind of titanium alloy pickle according to claim 1, it is characterized in that described determination of acid-basetitration fluotitanic acid content, its method is:
(1) accurately pipette titanium alloy pickle 5 ml in 100 ml plastics volumetric flasks, be diluted with water to scale, shake up,
(2) in above-mentioned dilution, pipette 5 ml in 250 ml conical flasks, in conical flask, add 10 ~ 20ml saturated potassium chloride solution, 15 ~ 30 ml absolute ethyl alcohols;
(3) in above-mentioned test solution, add 1 ~ 2 phenolphthalein indicator again, dripping 0.1039 mol/L NaOH standard solution pink to test solution change is terminal;
(4) above-mentioned test solution is heated to firm boiling, continuing dropping 0.1039 mol/L NaOH standard solution pink to test solution change is terminal, record consumption V
1.
3. the measuring method of fluohydric acid content in a kind of titanium alloy pickle according to claim 1, it is characterized in that described calcium chloride precipitation method measures total Oil repellent, its method is:
(1) pipette dynamic titanium alloy pickle 5 ml in 100 ml plastics volumetric flasks, be diluted with water to scale, shake up, in above-mentioned dilution, pipette 5 ml in 250ml beaker, and add 10 ~ 20 ml deionized waters;
(2) in beaker, drip 2 mol/L NaOH solution 3 ~ 5 ml, be heated to firm boiling, flowing water-cooled, be all transferred in suction funnel by cooled test solution, miillpore filter suction filtration obtains filtrate;
(3) gained filtrate is all transferred in 500 ml conical flasks, adds 1 ~ 2 methyl red indicator, first drip 6 mol/L hydrochloric acid micro-red to solution, then drip 0.1039 mol/L NaOH standard solution to test solution and just turn yellow as terminal;
(4) in above-mentioned test solution, 20 ml lime chloride standard solution are accurately added, 5 min are boiled in heating, after air cooling to room temperature, miillpore filter suction filtration obtains filtrate, filtrate is all transferred in 250 ml conical flasks, in above-mentioned test solution, add 2mol/L NaOH solution, add the 2 mol/L NaOH solution of 1.25 ml in every 10 ml test solutions, and add solid calcium indicator 0.05 g, dropping to solution with EDTA titrand, to become pure blue from claret be terminal, and record its consumption V
3.
4. the measuring method of fluohydric acid content in a kind of titanium alloy pickle according to claim 1-3, it is characterized in that: deduct the Oil repellent in the fluotitanic acid content of measurement with the total Oil repellent measured, obtain the fluohydric acid content in titanium alloy pickle, its concrete formula is as follows: fluohydric acid content is calculated as follows:
（1）。
5. the measuring method of fluohydric acid content in a kind of titanium alloy pickle according to claim 4, is characterized in that: wherein in (1) formula, C
hF---the concentration of hydrofluorite in titanium alloy pickle, g/L; C
1---the concentration of NaOH titrand, mol/L; V
1---the volume of the standard solution of sodium hydroxide consumed, ml; C
2---the concentration of lime chloride titrand, mol/L; V
2---the volume of the lime chloride titrand quantitatively added, ml; C
3---the concentration of EDTA titrand, mol/L; V
3---the volume of the EDTA standard solution consumed, ml; V
0---get the volume of tank liquor, ml; 20.01---the relative molar mass of HF, g/mol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105136975A (en) * | 2015-09-01 | 2015-12-09 | 武汉钢铁(集团)公司 | Method for determining content of calcium fluoride in fluorite |
| CN106442663A (en) * | 2016-11-30 | 2017-02-22 | 江西洪都航空工业集团有限责任公司 | Analysis method for hydrofluoric acid content in pickling solution |
| CN108375647A (en) * | 2018-03-02 | 2018-08-07 | 沈阳飞机工业（集团）有限公司 | A kind of titanium alloy etching tank liquid chemical analysis method |
| CN109580602A (en) * | 2018-11-29 | 2019-04-05 | 中国航发沈阳黎明航空发动机有限责任公司 | The method of inspection of fluorine ion in a kind of trade effluent |
| CN117001267A (en) * | 2023-05-31 | 2023-11-07 | 东莞市海发科技发展有限公司 | Workpiece renovating and repairing process |
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| CN117001267A (en) * | 2023-05-31 | 2023-11-07 | 东莞市海发科技发展有限公司 | Workpiece renovating and repairing process |
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