CN117607343A - Rapid detection method of neutral degreasing agent - Google Patents
Rapid detection method of neutral degreasing agent Download PDFInfo
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- CN117607343A CN117607343A CN202311486258.2A CN202311486258A CN117607343A CN 117607343 A CN117607343 A CN 117607343A CN 202311486258 A CN202311486258 A CN 202311486258A CN 117607343 A CN117607343 A CN 117607343A
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- degreasing agent
- degreasing
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- 238000005237 degreasing agent Methods 0.000 title claims abstract description 55
- 239000013527 degreasing agent Substances 0.000 title claims abstract description 52
- 230000007935 neutral effect Effects 0.000 title claims abstract description 23
- 238000001514 detection method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005238 degreasing Methods 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000012530 fluid Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011550 stock solution Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012085 test solution Substances 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- -1 hydrogen ions Chemical class 0.000 claims 1
- 238000004448 titration Methods 0.000 abstract description 10
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000010687 lubricating oil Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002956 ash Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The rapid detection method of neutral degreasing agent comprises the steps of quantitatively adding an acid solution into a certain volume of degreasing liquid, enabling the higher the degreasing agent concentration, the more the acid consumed by the reaction, namely, the higher the pH value, and vice versa, then carrying out nonlinear polynomial fitting on the measured pH value and the degreasing agent concentration to obtain a relation function of the pH value and the degreasing agent concentration, and further calculating the degreasing agent concentration in the field degreasing liquid by utilizing the relation function; the invention adopts the common laboratory equipment vessels such as a pH meter, an adjustable pipette, a volumetric flask and the like, does not need to use special equipment devices, and has low cost and simple and convenient operation; the method has the advantages of short operation flow, low requirement on personnel operation experience, easy grasp, effective shortening of the concentration adjustment time of the degreasing fluid, improvement of the working efficiency and solving of the problem of low accuracy of measuring the concentration of the neutral degreasing agent by a weight method and a titration method.
Description
Technical Field
The invention relates to the field of analysis and detection, in particular to a rapid detection method of a neutral degreasing agent.
Background
In degreasing processes for highly demanding metallic materials, such as precision copper belts, surface cleaning is typically performed with a degreasing agent at a suitable concentration to remove surface oil stains. To avoid corrosion of the metal surface by acidic or alkaline environments, it is desirable that the pH of the degreasing agent used be maintained neutral. The degreasing agent is usually compounded by a plurality of surfactants, penetrants and corrosion inhibitors, has a working pH value of about 7-8, and is widely applied to the production process of copper and copper alloy strips at present. The effective components of the degreasing agent are continuously lost along with the production process in the use process, so that the stock solution is required to be supplemented into the degreasing tank to ensure that the concentration of the degreasing solution in the degreasing tank is within a reasonable preset range, otherwise, the degreasing effect is directly influenced, and the surface quality is influenced.
The current detection methods for the concentration of the degreasing agent are a drying weighing method and a titration method, but the two methods have larger limitations. The detection period of the drying weighing method is longer, and because the degreasing fluid is mixed with more oil, ash, metal ions and other interference factors in the using process, the detection result is often higher, and the accuracy is lower. The titration method generally adopts hydrochloric acid or sulfuric acid standard solution, titrates alkaline components in consumed degreasing liquid, and is mostly applied to alkaline degreasing agents. For neutral degreasing agents, the pH value of the neutral degreasing agents is neutral, so that the volume of an acid-base standard solution consumed by a titration method is small, and the detection error is large. Titration methods require operators to have a certain literacy and operational experience. Guo Jiang et al disclose an industrial online automatic titration system and method for detecting the concentration of a degreasing agent, wei Fei et al disclose an online detection and control device for the concentration of a degreasing agent, and Guo Tingyi disclose a titration device for detecting the concentration of a degreasing agent. The basic principle of the method is a titration method, an alkaline degreasing agent is suitable for the method, the detection accuracy of the alkaline degreasing agent is poor, a special device is required to be used, and the universal applicability is not strong.
For the above reasons, a rapid detection method of neutral degreasing agent has been developed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a rapid detection method for a neutral degreasing agent, which has the advantages of short operation flow, low requirements on personnel operation experience, easiness in grasping, capability of completing the measurement of each sample within 2-3 minutes after the working curve fitting is completed in advance, effective shortening of the degreasing liquid concentration adjustment time, improvement of the working efficiency, continuous use of the working curve and the relation function for 1-2 months, good precision and accuracy, and capability of solving the problem of lower accuracy of measuring the concentration of the neutral degreasing agent by a weight method and a titration method.
In order to achieve the above purpose, the invention adopts the following technical scheme: the fast detection method of neutral degreasing agent includes adding acid solution quantitatively into degreasing liquid in certain volume, the higher the degreasing agent concentration, the more the acid consumed by the reaction, i.e. the higher the pH value, and vice versa, and then nonlinear polynomial fitting is carried out on the measured pH value and the degreasing agent concentration to obtain the relation function of the two, and the degreasing agent concentration in the field degreasing liquid is calculated by utilizing the relation function.
Further, the specific steps of the rapid detection method are as follows:
step one, preparing a working curve solution: in 8 100mL volumetric flasks, 0.50mL,1.00mL,1.50mL,2.00mL,2.50mL,3.00mL,3.50mL and 4.00mL degreasing agent stock solutions are respectively absorbed by an adjustable pipetting gun, diluted to scale by water, and uniformly mixed, the concentration of the working curve solution is respectively 0.50%,1.00%,1.50%,2.00%,2.50%,3.00%,3.50% and 4.00%;
step two, nonlinear fitting of a working curve: respectively adding acid solution into the 8 volumetric flasks by using an adjustable pipetting gun, adding the acid solution with the volume of 1.00-10.00 mL, uniformly mixing, respectively measuring the pH value of the liquid in the 8 volumetric flasks on a pH meter, carrying out 3-6-order nonlinear polynomial fitting by using Excel with the pH value as an abscissa and the concentration as an ordinate, and obtaining a working curve and a relation function of the working curve and the pH value; under the condition that the concentration of the acid solution does not change significantly, fitting a working curve and a relation function;
step three, measuring a sample: adding the degreasing liquid sample into a 100mL volumetric flask to a scale mark, adding an acid solution with the same volume and type as the working curve fitting, uniformly mixing, and measuring the pH value by a pH meter;
step four, calculating a result: substituting the measured pH value into a relation function obtained by pre-fitting, and rapidly calculating by using EXCEL or other calculation tools to obtain the concentration of the degreasing agent in the sample;
step five, daily quality monitoring: the degreasing agent stock solution is used for preparing a test solution with known concentration periodically every week, the test solution is measured according to the third step and the fourth step, and whether the working curve is re-manufactured or not is determined according to the deviation degree of the measured result and the known result, wherein the deviation is not more than 0.15%.
Further, the acid solution in the second step is one of hydrochloric acid and sulfuric acid, and the hydrogen ion concentration of the acid solution is 0.05-0.20mol/L.
Further, the accuracy of the pH meter is 0.01, and the pH meter has an automatic temperature compensation function.
Further, the order of the nonlinear polynomial fitting in the step two is determined by the sum of squares residuals of the working curves, that is, the smaller the calculated sum of squares residuals of the working curves is, the better the fitting effect is.
Further, the concentration and the volume of the acid solution in the third step are determined by a preset curve midpoint method, namely, the concentration is taken as a vertical axis, and the end point of the working concentration range of the degreasing agent is taken as the vertical axis midpoint; the pH is set on the horizontal axis, ph=4 is set on the midpoint of the horizontal axis, the pH value of the degreasing liquid is adjusted to be around 4 on the midpoint of the vertical axis, and the concentration and the volume of the acid solution to be added are determined by the amount of the consumed acid.
The beneficial effects of the invention are as follows: compared with the prior art, the invention adopts the common laboratory equipment vessels such as a pH meter, an adjustable pipette, a volumetric flask and the like, does not need to use special equipment devices, and has low cost and simple and convenient operation; the method has the advantages that the operation flow is short, the requirements on the operation experience of personnel are not high, the method is easy to grasp, after the working curve fitting is finished in advance, the measurement of each sample can be finished within 2-3 minutes, the concentration adjustment time of the degreasing fluid is effectively shortened, the working efficiency is improved, the working curve and the relation function can be continuously used for 1-2 months, and meanwhile, the method also has good precision and accuracy, and the problem that the accuracy of measuring the concentration of the neutral degreasing agent by a weight method and a titration method is low is solved; the present invention is not described in detail in the prior art.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a graph of an operating curve and a relationship function.
Detailed Description
The invention is further described in detail below with reference to examples and embodiments:
example 1
The analysis process of the concentration of the neutral degreasing agent for producing the copper plate and strip comprises the following steps:
1. preparation of working curve solution: in 8 100mL volumetric flasks, 0.50mL,1.00mL,1.50mL,2.00mL,2.50mL,3.00mL,3.50mL and 4.00mL degreasing agent stock solutions are respectively absorbed by an adjustable pipetting gun, diluted to scale by water, and uniformly mixed, the concentration of the working curve solution is respectively 0.50%,1.00%,1.50%,2.00%,2.50%,3.00%,3.50% and 4.00%;
2. nonlinear fitting of the working curve: adding 3.00mL of hydrochloric acid solution with the concentration of 0.10mol/Lde into the 8 volumetric flasks respectively by using an adjustable pipette, uniformly mixing, and respectively measuring the pH value of the liquid in the 8 volumetric flasks on a pH meter, wherein the measurement results are shown in Table 1;
TABLE 1 working Curve solution pH after acid addition
Performing 3-order-6-order nonlinear polynomial fitting by Excel with pH value as abscissa and concentration as ordinate, and obtaining a working curve and a relation function of the working curve and the working curve as shown in figure 1;
calculating residual square sums of 3-order and 6-order fitting respectively, wherein the residual square sum of the final 4-order fitting is 0.0050%, and taking 4-order fitting functions: y= -0.0369x 4 +0.8721x 3 -6.7989x 2 +22.655x-26.404；
3. Determination of the samples: adding a degreasing liquid sample to be detected into a 100mL volumetric flask to a scale mark, adding 3.00mL of hydrochloric acid solution with the concentration of 0.10mol/L, uniformly mixing, and measuring the pH value to be 4.05 by using a pH meter;
4. calculation of results: let the relation function y= -0.0369x 4 +0.8721x 3 -6.7989x 2 +22.655x-26.404 is edited into a formula in EXCEL software, the measured pH value of 4.08 is input into the edited formula, and the concentration of the degreasing fluid is automatically calculated to be 1.85%;
5. interference analysis
The degreasing fluid generally contains lubricating oil, ash and metal ions in addition to the degreasing agent; the ash content and the metal ion content are low, the consumption of hydrochloric acid is negligible, so that the interference condition of the lubricating oil can be ignored, the lubricating oil is cleaned from the metal surface after the degreasing fluid works for a long time, and the content can reach 2% -3%;
to examine the interference condition of the lubricating oil, three pre-prepared degreasing solutions with the concentration of 1.00%,2.00% and 3.00% are respectively transferred into a 100mL volumetric flask, diluted to a scale, respectively added with 3mL of lubricating oil, fully and uniformly shaken, the concentration of the degreasing agent is measured according to the method, and compared with a sample without the lubricating oil, and the results in the table 2 show that the influence of the lubricating oil in the degreasing solution on the detection result is negligible;
TABLE 2 interference test of lubricating oil addition
6. Repeatability test
Obtaining 3 parts of degreasing fluid at different time on a production site, measuring the concentration of the degreasing fluid for 6 times by using the method under the condition of repeatability, wherein the relative standard deviation RSD is between 0.85% and 1.17%, and the method has good precision, and the measurement result is shown in Table 3;
TABLE 3 repeatability test
7. Label recovery test
Taking 3 pre-detected degreasing liquid samples in 3 100mL volumetric flasks, respectively adding 1.00mL degreasing agent stock solution, measuring the concentration according to the method, calculating the standard adding recovery rate to evaluate the accuracy of the method, and the test result in the table 4 shows that the standard adding recovery rate is 98.52% -103.34%, and the method has higher accuracy and can meet the use requirement.
Table 4 labeled recovery test
The method for measuring the concentration of the neutral degreasing agent is adopted to measure the concentration of the neutral degreasing agent, the accuracy and precision of the method are good, the standard adding recovery rate meets the requirements, the measurement result is accurate and reliable, the cost of instruments and equipment used by the method is low, the operation is simple and convenient, the method is easy to master, the use of the degreasing liquid in the production process can be effectively guided, and the degreasing efficiency of the metal surface is improved. The concentration adjustment time of the degreasing fluid can be effectively shortened, and the working efficiency is improved.
Claims (6)
1. A rapid detection method of a neutral degreasing agent is characterized in that: and quantitatively adding an acid solution into a certain volume of degreasing fluid, wherein the higher the concentration of the degreasing agent is, the more acid is consumed by the reaction, namely, the higher the pH value is, and vice versa, then carrying out nonlinear polynomial fitting on the measured pH value and the degreasing agent concentration to obtain a relation function of the measured pH value and the degreasing agent concentration, and further calculating the degreasing agent concentration in the field degreasing fluid by using the relation function.
2. The method for rapidly detecting neutral degreasing agent according to claim 1, wherein: the rapid detection method comprises the following specific steps:
step one, preparing a working curve solution: in 8 100mL volumetric flasks, 0.50mL,1.00mL,1.50mL,2.00mL,2.50mL,3.00mL,3.50mL and 4.00mL degreasing agent stock solutions are respectively absorbed by an adjustable pipetting gun, diluted to scale by water, and uniformly mixed, the concentration of the working curve solution is respectively 0.50%,1.00%,1.50%,2.00%,2.50%,3.00%,3.50% and 4.00%;
step two, nonlinear fitting of a working curve: respectively adding acid solution into the 8 volumetric flasks by using an adjustable pipetting gun, adding the acid solution with the volume of 1.00-10.00 mL, uniformly mixing, respectively measuring the pH value of the liquid in the 8 volumetric flasks on a pH meter, carrying out 3-6-order nonlinear polynomial fitting by using Excel with the pH value as an abscissa and the concentration as an ordinate, and obtaining a working curve and a relation function of the working curve and the pH value; under the condition that the concentration of the acid solution does not change significantly, fitting a working curve and a relation function;
step three, measuring a sample: adding the degreasing liquid sample into a 100mL volumetric flask to a scale mark, adding an acid solution with the same volume and type as the working curve fitting, uniformly mixing, and measuring the pH value by a pH meter;
step four, calculating a result: substituting the measured pH value into a relation function obtained by pre-fitting, and rapidly calculating by using EXCEL or other calculation tools to obtain the concentration of the degreasing agent in the sample;
step five, daily quality monitoring: the degreasing agent stock solution is used for preparing a test solution with known concentration periodically every week, the test solution is measured according to the third step and the fourth step, and whether the working curve is re-manufactured or not is determined according to the deviation degree of the measured result and the known result, wherein the deviation is not more than 0.15%.
3. The method for rapidly detecting neutral degreasing agent according to claim 2, wherein: the acid solution in the second step is one of hydrochloric acid and sulfuric acid, and the concentration of hydrogen ions in the acid solution is 0.05-0.20mol/L.
4. The method for rapidly detecting neutral degreasing agent according to claim 1, wherein: the accuracy of the pH meter is 0.01, and the pH meter has an automatic temperature compensation function.
5. The method for rapidly detecting neutral degreasing agent according to claim 2, wherein: the order of the nonlinear polynomial fitting in the second step is determined by the sum of squares of residuals of the working curves, namely the smaller the calculated sum of squares of residuals of the working curves is, the better the fitting effect is.
6. The method for rapidly detecting neutral degreasing agent according to claim 2, wherein: the concentration and the volume of the acid solution in the third step are determined by a preset curve midpoint method, namely, the concentration is taken as a vertical axis, and the end point of the working concentration range of the degreasing agent is taken as a vertical axis midpoint; the pH is set on the horizontal axis, ph=4 is set on the midpoint of the horizontal axis, the pH value of the degreasing liquid is adjusted to be around 4 on the midpoint of the vertical axis, and the concentration and the volume of the acid solution to be added are determined by the amount of the consumed acid.
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| CN202311486258.2A CN117607343A (en) | 2023-11-09 | 2023-11-09 | Rapid detection method of neutral degreasing agent |
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