Some standard content:
Record number: 2781-1999
HG/T 3593-1999
This standard has one level and six indicators: copper content, iron content, acid insoluble content, solubility in potassium pyrophosphate solution, lead content and Hull cell test.
This standard was proposed by the Technical Supervision Department of the former Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Inorganic Chemical Branch of the National Technical Committee for Chemical Standardization. The drafting units of this standard are: Tianjin Chemical Research and Design Institute of the Ministry of Chemical Industry, and Electrochemical Industry Research Institute of Xiangfan City, Hubei Province. The main drafters of this standard are: Su Peiji and Zhao Chengxian. This standard is entrusted to the Inorganic Chemical Branch of the National Technical Committee for Chemical Standardization for interpretation. 1115
1 Scope
Chemical Industry Standard of the People's Republic of China
Cupric pyrophosphate for electroplating use
Cupric pyrophosphate for electroplating useHG/T 3593—1999
This standard specifies the requirements, test methods, inspection rules, marking, labeling, packaging, transportation and storage of copper pyrophosphate for electroplating use. This standard applies to copper pyrophosphate for electroplating. It is mainly used for cyanide-free electroplating. Molecular formula: CuzP,O,,3H20
Relative molecular mass: 355.08 (according to the 1995 international relative atomic mass) 2 Referenced standards
The provisions contained in the following standards constitute the provisions of this standard through reference in this standard. When this standard is published, the versions shown are valid. All standards will be revised, and parties using this standard should explore the possibility of using the latest version of the following standards. GB/T 601 —1988
GB/T 602-—1988
GB/T 603-1988
GB/T 1250--1989
Chemical reagents-Preparation of standard solutions for titration analysis (volumetric analysis) Chemical reagents
Preparation of standard solutions for determination of impurities (neqISO6353-1:1982) Preparation of preparations and products used in test methods (negISO6353-1:1982) Chemical reagent meters
Methods for expressing and determining limit values GB/T 3049—1986
General method for determination of iron content in chemical products (1982)
GB/T 6678--1986
GB/T6682--1992
GB/T 9723—1988
3 Requirements
General rules for sampling of chemical products
Phenanthroline spectrophotometry (eqvISO6685: Specifications and test methods for water used in analytical laboratories (eqyISO3696:1987) Chemical reagents Flame atomic absorption spectrometry General rules 3.1 Appearance: light blue powder or block.
3.2 Copper pyrophosphate for electroplating shall comply with the requirements of Table 1. Table 1 Requirements
Copper (Cu ) content/%
Iron (Fe) content/%
Acid insoluble matter content/%
Solubility in potassium pyrophosphate solution/%
Lead (Pb) content/%
Hull cell test (electroplating under D≥10A/dm2)Approved by the State Administration of Petroleum and Chemical Industry on April 20, 19991116
Implemented on April 1, 2000
4Test method
HG/T 3593-1999
The reagents and water used in this standard, unless otherwise specified, refer to analytical reagents and grade 3 water specified in GB/T6682. The standard titration solutions, impurity standard solutions, preparations and products used in the test, unless otherwise specified, are prepared in accordance with the provisions of GB/T601, GB/T602 and GB/T603.
Safety Tips: The hydrochloric acid and sodium hydroxide used in the test are corrosive products, so be careful when operating! 4.1 Determination of Copper Content
4.1.1 Method Summary
Under slightly acidic conditions, an appropriate amount of potassium iodide added to the sample reacts with divalent copper to precipitate an equivalent amount of iodine. The precipitated iodine is titrated with sodium thiosulfate standard titration solution, starch is used as an indicator, and the end point is determined by the color change. 4.1.2 Reagents and Materials
4.1.2.1 Potassium iodide;
4.1.2.2 Sodium pyrophosphate;
4.1.2.3 Sulfuric acid solution: 1+1;
Acetic acid solution: 4+1;
4. 1. 2. 4
4.1.2.5 Potassium thiocyanate solution: 100g/L;4.1.2.6 Sodium thiosulfate standard titration solution: c(NazS,03) about 0.1mol/L;4.1.2.7 Starch indicator solution: 10g/L (use period is two weeks). 4.1.3 Analysis steps
Weigh 5g of sample (accurate to 0.0002g), place in a 250mL beaker, add 20ml sulfuric acid solution and 20ml water to dissolve the sample, and heat until white smoke appears. After cooling, dissolve with 50mL water, transfer to a 250mL volumetric flask, add water to the scale, shake and hook, this solution is test solution A. Reserve this solution for the determination of iron
Use a pipette to transfer 20mL of test solution A, place in a 250mL conical flask, add 1g of sodium pyrophosphate, shake to dissolve it completely, add 2g of potassium iodide and 10mL of acetic acid solution, immediately titrate with sodium thiosulfate standard titration solution until the solution turns light yellow, add 1mL of starch solution, continue to titrate until light blue, add 10mL of potassium thiocyanate solution, and finally titrate until the blue color just disappears. Perform a blank test at the same time.
4.1.4 Expression of analysis results
The copper (Cu) content (X,) expressed as mass fraction is calculated according to formula (1): X = c(VV.)X0. 063 55 ×100
m×250
Wherein:
actual concentration of sodium thiosulfate standard titration solution, mol/L; -volume of sodium thiosulfate standard titration solution consumed by titration test solution, mL; -volume of sodium thiosulfate standard titration solution consumed by titration blank test solution, mLV.-
m--mass of sample, g;
·(1)
0.06355——mass of copper in grams equivalent to 1.00ml of sodium thiosulfate standard titration solution [c(NazSzO3)=1.000mol/L].
4.1.5 Allowable difference
The arithmetic mean of the results of two parallel determinations shall be taken as the determination result. The absolute difference of the parallel determination results shall not exceed 0.2%. 4.2 Determination of iron content
4.2.1 Summary of method
Same as Chapter 2 of GB/T3049--1986.
4.2.2 Reagents and materials
Same as Chapter 3 of GB/T3049-1986 and
4.2.2.1 Ammonium chloride.
4.2.2.2 Nitric acid solution: 1+2.
4.2.2.3 Washing liquid.
HG/T 3593—1999
Preparation: Weigh 5g of ammonium chloride, dissolve it in an appropriate amount of water, add 5ml of ammonia water, and dilute it to 100mL with water. 4.2.3 Instruments and equipment
Spectrophotometer: with an absorption cell of 3 cm thickness. 4.2.4 Analysis steps
4.2.4.1 Drawing of standard curve
According to the provisions of 5.3 of GB/T3049~-1986, select an absorption cell of 3 cm thickness and the corresponding amount of iron standard solution to draw the standard curve.
4.2.4.2 Preparation of blank test solution
According to the method of preparing test solution A in 4.1.3, perform the operation without adding sample. 4.2.4.3 Determination
Use a pipette to transfer 25 mL of test solution A (4.1.3) and blank test solution respectively, place them in 250 mL beakers, add 0.5 mL of nitric acid solution, boil for 2 min, add 1.5 g of ammonium chloride, add 1+2 ammonia solution dropwise until the generated precipitate dissolves, heat on a water bath for 30 min, filter with ash-free filter paper, wash the precipitate with washing liquid until the blue color on the filter paper disappears completely, wash with hot water 3 times, dissolve the precipitate with 3 ml of 1+1 hot hydrochloric acid solution, wash the filter paper with 10 mL of water, collect the filtrate and washing liquid, neutralize with 1+2 ammonia solution, add 3 drops of 1+1 hydrochloric acid solution, and operate according to the provisions of 5.4 of GB/T3049-1986 from "If necessary, add water to 60 mL" to ". Measure its absorbance".
Subtract the absorbance of the reagent blank solution from the absorbance of the test solution, and find the corresponding iron content from the curve. 4.2.5 Expression of analytical results
Iron (Fe) content expressed as mass fraction (X,) Calculate according to formula (2): X2
×100=
25×1000
m×250
Where: ml—the mass of iron found on the curve, mg; m—the mass of the sample, g.
4.2.6 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference of the parallel determination results shall not exceed 0.003%. 4.3 Determination of acid-insoluble matter content
4.3.1 Method summary
The sample is dissolved in sulfuric acid, and the insoluble matter is filtered, washed, dried and weighed. 4.3.2 Reagents and materials
Sulfuric acid solution: 1 + 1.
4.3.3 Instruments and equipmentbZxz.net
Glass sand: pore size 5μm~15μm.
4.3.4 Analysis steps
Weigh about 20g of sample (accurate to 0.1g), place it in a 500mL beaker, add 50mL sulfuric acid solution to dissolve, filter it with a glass sand crucible dried to constant weight at 105℃~110℃, wash it until it is neutral (check with pH test paper), and place the glass sand crucible in a drying oven at 105℃~110℃ to dry it to constant weight.
4.3.5 Expression of analysis results
The acid-insoluble content (X:) expressed as mass fraction is calculated according to formula (3): 1118
Where: m1-mass of glass sand crucible, g; HG/T 3593-1999
ml×100
m2Mass of glass sand and acid-insoluble matter, g; Mass of sample, g.
4.3.6 Allowable difference
The arithmetic mean of the parallel determination results shall be taken as the determination result. The absolute difference of the parallel determination results shall not exceed 0.02%. 4.4 Solubility of copper pyrophosphate in potassium pyrophosphate solution 4.4.1 Reagents and materials
Potassium pyrophosphate
4.4.2 Instruments and equipment
Glass casserole: pore size 5μm~15μm.
4.4.3 Analysis steps
(3)
Weigh 200g potassium pyrophosphate (accurate to 0.01g), dissolve it in 400ml water, then weigh 50g copper pyrophosphate sample (accurate to 0.01g), add it to the potassium pyrophosphate solution and dissolve it fully. Filter with a glass crucible that has been kept at constant weight at 105℃~~110℃, wash until neutral (check with pH test paper), and place the glass crucible in a drying oven at 105℃~110℃ to dry until constant weight. 4.4.4 Expression of analysis results
The solubility of copper pyrophosphate in potassium pyrophosphate solution expressed as mass fraction (X.) is calculated according to formula (4): ml×100
Where: mt—mass of glass crucible, g; m2
Mass of glass crucible and insoluble matter, g;
Mass of sample, g.
4.4.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference of the parallel determination results shall not exceed 0.02%. 4.5 Determination of lead content
4.5.1 Summary of the method
Same as Chapter 3 of GB/T9723--1988.
4.5.2 Reagents and materials
4.5.2.1 Sulfuric acid solution: 1+1;
4.5.2.2 Lead standard solution: 1mL solution contains 0.1mgPb. 4.5.3 Instruments and equipment
4.5.3.1 Atomic absorption spectrophotometer;
4.5.3.2 Light source: lead hollow cathode lamp.
4.5.4 Analysis steps
Weigh 25g of sample (accurate to 0.01g), place in a 250mL beaker, add 50mL sulfuric acid solution to dissolve the sample, and heat until white smoke appears. After cooling, dissolve it with 50mL water, transfer it to a 250mL volumetric flask, add water to the scale, and shake it. Use a pipette to transfer 25mL of the test solution respectively, place it in 4 100mL volumetric flasks, then use a pipette to add 0mL, 1mL, 2mL, and 3mL of lead standard solution respectively, dilute with water to the scale, and shake it. On an atomic absorption spectrophotometer, use an air-acetylene flame, adjust to zero with water at a wavelength of 283.3nm, and measure the absorbance of the above solution. Draw a curve with the concentration of standard lead added as the horizontal axis and the corresponding absorbance as the vertical axis. Extend the curve in the opposite direction to intersect with the horizontal axis. The concentration of lead at the intersection is the concentration of lead in the test solution. 4.5.5 Expression of analysis results
HG/T 3593--1999
The lead (Pb) content (X,) expressed as mass fraction is calculated according to formula (5): X
c × 100
Wherein: C——lead concentration of the test solution obtained from the curve, μg/mL; m
…-mass of the sample, g.
4.5.6 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference of the parallel determination results shall not exceed 0.001%. 4.6 Hull test
4.6.1 Reagents and materials
4.6.1.1 Potassium pyrophosphate;
4.6.1.2 Pyrophosphoric acid;
4.6.1.3 Potassium hydroxide solution: 6g/L.
4.6.2 Instruments and equipment
4.6.2.1 Hull cell: 250mL, the Hull cell test device is shown in Figure 1; o
Figure 1 Hull cell test device diagram
4.6.2.2 Electroplating test power supply: single-phase half-wave 10A/12V; 4.6.2.3 Steel plate: (1~2)mm×70mm×100mm, degreased and derusted, with a smooth and flat surface; 4.6.2.4 Pure copper plate: (1~2)mm×70mm×63mm, degreased and derusted, with a smooth and flat surface; 4.6.2.5 Constant temperature water bath.
4.6.3 Test conditions
4.6.3.1 Temperature: (48±2)℃;
4.6.3.2 pH value of electroplating solution: 8.8±0.2. 4.6.4 Analysis steps
4.6.4.1 Preparation of electroplating test solution
Weigh 400g potassium pyrophosphate (accurate to 0.1g), dissolve it in water, then add 100g copper pyrophosphate sample (accurate to 0.1g) to the solution, then add water to 1000mL, and adjust the pH of the solution to 8.8±0.2 with pyrophosphoric acid or potassium hydroxide solution (check with precision pH test paper or pH meter).
4.6.4.2 Determination
Take 500mL of the electroplating test solution, heat it to 50℃, take 250mL and place it in a Hull cell. Place the cell in a constant temperature water bath and control the temperature to (48±2)℃. Use a steel plate as the cathode and a pure copper plate as the anode. Start electroplating with a current of 2A for 2min. When the time is up, turn off the power, take out the cathode plate, wash it with pure water, dry it, and measure the width of the poor coating (i.e. the distance from the point of maximum current density of the good coating to the edge of the anode) at half the height of the coating.
The current density D is calculated according to formula (6):
HG/T 3593-1999
Dk I(5. 10 -- 5. 24lgL)
Wherein: Dk---the maximum current density of the good coating area on the cathode plate in the Hull cell test, A/dm2; I---the current intensity indicated by the ammeter in the test, A; L---the distance between the edge of the cathode plate near the anode end and the edge of the good coating in the Hull cell test, cm. If the current density Dk ≥ 10A/dm2 and the coating is good, the product can be considered to meet the requirements of this standard. 5 Inspection rules
5.1 All items specified in this standard are routine test items. 5.2 Each batch of products shall not exceed 5t.
5.3 Determine the number of sampling units in accordance with 6.6 of GB/T6678-1986. When sampling, insert the sampler obliquely from the top of the packaging bag to 3/4 of the depth of the material layer to take a sample. After mixing the collected samples, reduce them to no less than 500g according to the quartering method, and pack them in two clean and dry wide-mouth bottles with stoppers and seal them. Paste labels on the bottles, indicating: manufacturer name, product name, batch number, sampling date and name of the sampler. One bottle is used for inspection and the other bottle is kept for three months for reference. 5.4 Copper pyrophosphate for electroplating should be inspected by the quality supervision and inspection department of the manufacturer in accordance with the provisions of this standard. The manufacturer should ensure that all copper pyrophosphate for electroplating shipped from the factory meets the requirements of this standard. 5.5 If one of the indicators in the inspection results does not meet the requirements of this standard, re-sampling should be carried out from twice the amount of packaging for re-inspection. If even one of the indicators in the re-inspection results does not meet the requirements of this standard, the entire batch of products will be unqualified. 5.6 The rounded value comparison method specified in 5.2 of GB/T1250-1989 is used to determine whether the test results meet the standards. 6 Marking and labeling
6.1 The packaging of copper pyrophosphate for electroplating should have firm and clear markings, including: manufacturer name, factory address, product name, trademark, net content, batch number or production date, shelf life, and this standard number. 6.2 Each batch of copper pyrophosphate electroplating products shipped out of the factory should be accompanied by a quality certificate, including: manufacturer name, factory address, product name, trademark, net content, batch number or production date, shelf life, proof that the product quality complies with this standard and the number of this standard. 7 Packaging, transportation, storage
7.1 The inner packaging of copper pyrophosphate electroplating is a polyethylene plastic film bag with a thickness of not less than 0.05mm. The outer packaging is a plastic woven bag. The net content of each bag is 25kg.
The inner bag is tied twice with nylon rope, or sealed with other equivalent methods; the outer bag is folded at a distance of not less than 30mm from the edge of the bag, and the outer bag is sewn with vinyl nylon thread or other threads of equivalent quality at a distance of not less than 15mm from the edge of the bag. The stitches are neat and the stitches are evenly hooked. There is no leakage or skipping.
7.2 Copper pyrophosphate electroplating should be covered during transportation to prevent rain and moisture. 7.3 Copper pyrophosphate for electroplating should be stored in a cool and dry place to avoid rain and moisture. 7.4 The product has a shelf life of six months from the date of production under the packaging, transportation and storage conditions of this standard. If the shelf life is exceeded, it should be re-inspected to see if it meets the requirements of this standard.
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