CN114112837B - Method for detecting porosity of coating - Google Patents

Method for detecting porosity of coating Download PDF

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CN114112837B
CN114112837B CN202111341111.5A CN202111341111A CN114112837B CN 114112837 B CN114112837 B CN 114112837B CN 202111341111 A CN202111341111 A CN 202111341111A CN 114112837 B CN114112837 B CN 114112837B
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dryer
sample
solution
sodium sulfide
porosity
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CN114112837A (en
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李辉东
王晓伟
周德松
康利铭
许英才
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China Aviation Optical Electrical Technology Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/088Investigating volume, surface area, size or distribution of pores; Porosimetry

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Abstract

The invention relates to a method for detecting the porosity of a plating layerThe method comprises the steps of preparing sodium sulfide solution and potassium dihydrogen phosphate solution, adding the sodium sulfide solution into a dryer, placing a partition plate, placing a sample on a nylon net tray and on the partition plate of the dryer, passing one end of a latex tube through a rubber plug on a cover of the dryer and a round hole on the partition plate, connecting the other end of the latex tube with the bottom of a funnel, fixing the funnel on a iron stand, adding the potassium dihydrogen phosphate solution into the dryer through the funnel to react with the sodium sulfide solution to generate hydrogen sulfide atmosphere with the concentration of 0.75+/-0.25 ppm, and placing the sample in H 2 And (3) placing the sample in the S atmosphere at room temperature for 48 hours plus or minus 2 hours, taking out the sample, and judging whether the porosity of the sample is qualified according to whether spots are generated on the surface of the gold-plated layer of the sample. The invention utilizes the existing simple equipment and reagents, can simulate the failure phenomenon that corrosion occurs in the air to generate rust spots in the later stage placing and using process of the copper alloy gold-plated part, and overcomes the defects of the conventional test method for the porosity of the gold-plated part.

Description

Method for detecting porosity of coating
Technical Field
The invention relates to the technical field of connectors, in particular to a method for detecting the porosity of a coating.
Background
The copper matrix gold plating belongs to a typical cathode plating, and tiny pores exist when the thickness of the gold layer is smaller than 3 mu m. For cost reasons, the gold plating thickness of gold plated connectors is typically no more than 3 μm. In the subsequent storage or use process, the bottom plating layer or the copper matrix may oxidize with O, S elements in the air through the micropores, so as to generate red or black spots. With the continuous development of industrialization, the influence of S element in air is more and more obvious. The corrosion resistance of the product to the S element cannot be effectively identified by the conventional test of the corrosion resistance of the gold plating layer, such as neutral salt spray resistance, damp heat resistance, nitric acid corrosion resistance and the like. Although the technology of mixed gas corrosion test, sulfurous acid fumigation test and the like is adopted in the industry to carry out the test for accelerating the long spots, the equipment required by the test is expensive, and special gas composition control or an advanced counting microscope is required, so that the test is not easy to realize and implement. Therefore, a simple and effective acceleration test detection method is urgently needed, and the situation that spots are generated by corrosion of S element in the later placement and use process of the copper alloy gold-plated part is simulated, so that the porosity of a gold-plated layer is identified, and whether a product is qualified is identified.
Disclosure of Invention
In order to solve the problems, the invention provides a method for detecting the porosity of a plating layer, which can simulate the failure phenomenon that rusted spots are generated by corrosion of sulfur elements in the air in the later-stage placing and using processes of a copper alloy gold-plated part by using the existing simple equipment and reagents, and overcomes the defects of the conventional method for testing the porosity of the gold-plated part.
The invention is realized by the following technical scheme, and the method for detecting the porosity of the coating provided by the invention comprises the following steps:
(1) Adding a certain amount of deionized water into a beaker I, and adding analytically pure sodium sulfide Na 2 S·9H 2 Adding O into a beaker I to dissolve the O to prepare sodium sulfide solution;
(2) Adding a certain amount of deionized water into a beaker II, and adding analytically pure potassium dihydrogen phosphate KH 2 PO 4 Adding the solution into a beaker II to dissolve the solution to prepare a monopotassium phosphate solution;
(3) Adding the sodium sulfide solution dissolved in the step (1) into a dryer, and then placing a dryer partition board into the dryer, wherein the dryer partition board is at a certain distance from the bottom of the dryer and is not contacted with the sodium sulfide solution;
(4) Placing one or more gold-plated part samples to be tested on a nylon net tray, wherein the samples are not contacted with each other; then placing the nylon net tray and the sample to be tested on the nylon net tray on a dryer separator;
(5) One end of the emulsion tube passes through a rubber plug on a dryer cover and a round hole on a partition plate in the dryer, and is inserted into the bottom of the dryer, and the space between the dryer cover and the dryer is covered and sealed by vacuum grease; the other end of the emulsion tube is connected with the bottom of the funnel, and the funnel is fixed on the iron stand;
(6) Adding the monopotassium phosphate solution prepared in the step (2) to the bottom of a dryer through a funnel and a latex tube to react with sodium sulfide solution, and immediately clamping the latex tube with a water stop clamp to seal after the monopotassium phosphate solution is added, so that the inside of the dryer is ensured to be in a sealed environment;
finally, the sodium sulfide solution prepared in the step (1) and the monopotassium phosphate solution prepared in the step (2) are reacted in a dryer, and H with the concentration of 0.75+/-0.25 ppm is generated in the sealed dryer 2 S atmosphere, H at the concentration of the sample on the nylon net tray 2 And (3) placing the sample in the S atmosphere for 48 hours plus or minus 2 hours at room temperature, taking out the sample, observing the condition that spots are generated on the gold-plating layer of the sample by using a 10-time magnifying glass, and judging whether the porosity of the sample is qualified according to whether spots are generated on the surface of the gold-plating layer of the sample.
Further, step (1) is to add 30g of analytically pure sodium sulfide Na 2 S·9H 2 O was added to 300ml of deionized water to dissolve it to prepare a sodium sulfide solution.
Further, step (2) is to add 3.5g of analytically pure potassium dihydrogen phosphate KH 2 PO 4 To 200ml of deionized water was added to dissolve the solution to prepare a potassium dihydrogen phosphate solution.
Further, in the method for detecting the porosity of the plating layer, a glass dryer with a caliber of 240mm can be selected.
The beneficial technical effects of the invention are as follows:
the method for testing the porosity of the copper alloy gold-plated part by adopting the hydrogen sulfide atmosphere corrosion method can effectively simulate the fault phenomenon that the copper alloy gold-plated part is corroded by sulfur element to generate rusted spots in the process of placing and using in the air, can be used as an acceleration test of the corrosion condition of the copper alloy gold-plated part in sulfur-containing air, and overcomes the defects of the conventional method for testing the porosity of the gold-plated part. The used medicines and appliances are conventional equipment, so that the cost is low, and the implementation are easy. The joint of the drier and the cover is sealed by vacuum grease, and the sealing is carried out by clamping the latex tube by a water stop clamp after the potassium dihydrogen phosphate solution is added, so that the leakage of hydrogen sulfide gas in the drier can be avoided. After the dryer is sealed, the second medicine is added through the funnel, so that the generated hydrogen sulfide can be ensured to be sealed in the dryer, and the repeatability of the test is good. The method can control the concentration of generated hydrogen sulfide by controlling the amounts of sodium sulfide and potassium dihydrogen phosphate, and can be used for detecting the porosity of the gold-plating layer under different application environments.
Drawings
FIG. 1 is a schematic diagram of a detection device according to the present invention.
1-dryer, 2-dryer partition plate, 3-latex tube, 4-rubber plug, 5-water stop clamp, 6-funnel, 7-iron ring, 8-iron stand, 9-sample, 10-nylon net tray.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
The device used in the method comprises an iron stand, a dryer, a latex tube, a water stop clamp, a funnel, a beaker, a nylon net tray, an iron ring and the like, which are all common equipment devices in chemical experiments. The latex tube and the rubber plug are sealed and airtight.
The specific method for detecting the porosity of the plating layer comprises the following steps:
(1) 300ml of deionized water was added to beaker I and 30g of analytically pure sodium sulfide Na 2 S·9H 2 O is added into 300ml of deionized water to be dissolved to prepare sodium sulfide solution;
(2) 200ml of deionized water was added to beaker II and 3.5g of analytically pure potassium dihydrogen phosphate KH 2 PO 4 Adding the solution into 200ml of deionized water to dissolve the solution to prepare a monopotassium phosphate solution;
(3) Adding the sodium sulfide solution dissolved in the step (1) into a dryer, and placing a dryer partition plate into the dryer, wherein the dryer partition plate is at a certain distance from the bottom of the dryer and is not contacted with the sodium sulfide solution;
(4) Placing one or more copper alloy gold-plated part samples to be tested on a nylon net tray, wherein the samples are not contacted with each other; then placing the nylon net tray and the sample to be tested on the nylon net tray on a separator of a dryer;
(5) One end of the emulsion tube passes through a rubber plug on a dryer cover and a round hole on a partition plate in the dryer, and is inserted into the bottom of the dryer, and the space between the dryer cover and the dryer is covered and sealed by vacuum grease; the other end of the latex tube is connected with the bottom of the funnel, the funnel is placed on the iron ring, and the iron ring is fixed on the iron stand;
(6) Adding the monopotassium phosphate solution prepared in the step (2) into the bottom of a dryer through a funnel and a latex tube to perform chemical reaction with sodium sulfide solution to generate hydrogen sulfide gas; immediately after the potassium dihydrogen phosphate solution is added, a sealing clamp is used for clamping and sealing the position, close to the rubber plug at the top of the dryer cover, on the latex tube, so as to ensure that the inside of the dryer is in a sealed environment;
finally, the 300ml of sodium sulfide solution prepared in step (1) was completely reacted with 200ml of potassium dihydrogen phosphate solution prepared in step (2), yielding H at a concentration of 0.75.+ -. 0.25ppm in a sealed desiccator 2 S atmosphere (hydrogen sulfide atmosphere concentration is tested by a commercial hydrogen sulfide gas detector), and H of a copper alloy gold-plated part sample on a nylon net tray at the concentration 2 And (3) placing the sample in the S atmosphere for 48 hours plus or minus 2 hours at room temperature, taking out the sample, observing the condition that spots are generated on the surface of the sample gold-plating layer by using a 10-time magnifying glass, and identifying whether the porosity of the sample is qualified according to whether spots are generated on the surface of the sample gold-plating layer or not: if spots exist, the porosity of the sample is judged to be unqualified, and the later copper alloy gold-plated part is extremely easy to be corroded by S element to generate rusted spots in the placing and using processes; if no spots exist, the porosity of the sample is judged to be qualified, and the copper alloy gold-plated part can meet the requirements of later-stage placement and use within a certain time range.
It should be noted that the present invention provides only one specific example, and in other examples, when the dryer volume is larger, the amount of sodium sulfide and potassium dihydrogen phosphate to be added to the dryer is increased, and at this time, the concentrations of the sodium sulfide solution and the potassium dihydrogen phosphate solution added to the dryer may be identical to those of the sodium sulfide solution and the potassium dihydrogen phosphate solution in the foregoing examples, but the concentration of the hydrogen sulfide atmosphere generated in the dryer should be finally ensured to be 0.75±0.25ppm. The detection concentration is the most suitable detection concentration verified by the test, if the concentration of the hydrogen sulfide atmosphere is more than 0.75 plus or minus 0.25ppm, the detection condition is too severe, and all copper alloy gold-plated parts can generate spots after being placed in the hydrogen sulfide atmosphere for 48 hours plus or minus 2 hours at room temperature; if the concentration of the hydrogen sulfide atmosphere is less than 0.75 plus or minus 0.25ppm, all copper alloy gold-plated parts do not generate spots after being placed in the hydrogen sulfide atmosphere for 48 hours plus or minus 2 hours at room temperature, so that 0.75 plus or minus 0.25ppm is selected as the most accurate detection concentration.
The plating layer is formed by continuously depositing metal atoms, and gaps among the metal atoms are normal phenomenon. The thicker the coating, the more fully the gaps between the metal atoms are mutually overlapped, and the smaller the relative porosity is. In the test process, the corrosive gas does not corrode to the matrix through the pores within a specified time range, so that the porosity is qualified. Theoretically, as long as the time is enough, the concentration is large enough, and micropores existing in the gold-plating layer are always corroded. The plating layer with small porosity has better corrosion resistance, and longer corrosion resistance time.
The method disclosed by the invention overcomes the defects of the prior art, is mainly applied to the rapid detection of the porosity of the copper alloy gold-plated plug connector with the plating thickness smaller than 3 mu m, and the test sample such as the gold-plated plug connector can judge the corrosion resistance of a gold-plated layer by conventional test technologies such as neutral salt spray resistance, damp heat resistance, nitric acid corrosion resistance and the like at present, but the test technologies cannot rapidly and effectively identify the corrosion resistance of the test sample to S element in the later use process. The test means of the corrosion resistance of the sample to the S element adopted in the current industry are completed by high equipment, and the test method has a long period and cannot be rapidly judged. The technology fills the blank in the aspect, utilizes the existing simple equipment and reagents, can simulate the environment of the later sample placing and using process, simulates the fault phenomenon that the copper alloy gold-plated part is corroded by the S element to generate rust spots in the placing and using process, is used as an accelerated test of the copper alloy gold-plated part in sulfur-containing air corrosion, and overcomes the defects of the conventional gold-plated part porosity test method.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.

Claims (4)

1. The method for detecting the porosity of the coating is characterized by comprising the following steps of:
(1) Adding a certain amount of deionized water into a beaker I, and adding analytically pure sodium sulfide Na 2 S·9H 2 Adding O into a beaker I to dissolve the O to prepare sodium sulfide solution;
(2) Adding a certain amount of deionized water into a beaker II, and adding analytically pure potassium dihydrogen phosphate KH 2 PO 4 Adding the solution into a beaker II to dissolve the solution to prepare a monopotassium phosphate solution;
(3) Adding the sodium sulfide solution dissolved in the step (1) into a dryer, and then placing a dryer partition board into the dryer, wherein the dryer partition board is at a certain distance from the bottom of the dryer and is not contacted with the sodium sulfide solution;
(4) Placing one or more gold-plated part samples to be tested on a nylon net tray, wherein the samples are not contacted with each other; then placing the nylon net tray and the sample to be tested on the nylon net tray on a dryer separator;
(5) One end of the emulsion tube passes through a rubber plug on a dryer cover and a round hole on a partition plate in the dryer, and is inserted into the bottom of the dryer, and the space between the dryer cover and the dryer is covered and sealed by vacuum grease; the other end of the emulsion tube is connected with the bottom of the funnel, and the funnel is fixed on the iron stand;
(6) Adding the monopotassium phosphate solution prepared in the step (2) to the bottom of a dryer through a funnel and a latex tube to react with sodium sulfide solution, and immediately clamping the latex tube with a water stop clamp to seal after the monopotassium phosphate solution is added, so that the inside of the dryer is ensured to be in a sealed environment;
finally, the sodium sulfide solution prepared in the step (1) and the monopotassium phosphate solution prepared in the step (2) are reacted in a dryer, and H with the concentration of 0.75+/-0.25 ppm is generated in the sealed dryer 2 S atmosphere, H at the concentration of the sample on the nylon net tray 2 And (3) placing the sample in the S atmosphere for 48 hours plus or minus 2 hours at room temperature, taking out the sample, observing the condition that spots are generated on the gold-plating layer of the sample by using a 10-time magnifying glass, and judging whether the porosity of the sample is qualified according to whether spots are generated on the surface of the gold-plating layer of the sample.
2. The method for detecting porosity of plating layer according to claim 1, wherein in the step (1), 30g of analytically pure sodium sulfide Na 2 S·9H 2 O was added to 300ml of deionized water to dissolve it to prepare a sodium sulfide solution.
3. The method for detecting the porosity of a plating layer according to claim 1, wherein in the step (2), 3.5g of analytically pure potassium dihydrogen phosphate KH 2 PO 4 To 200ml of deionized water was added to dissolve the solution to prepare a potassium dihydrogen phosphate solution.
4. A method for detecting porosity of a coating according to any one of claims 1 to 3, characterized in that a glass drier with a caliber of 240mm is selected.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102116730A (en) * 2010-12-09 2011-07-06 中兴通讯股份有限公司 Method for testing porosity of electric connector gold-plating layer
CN102393427A (en) * 2011-11-02 2012-03-28 山西太钢不锈钢股份有限公司 Analyzing method of Ni content in melted steel ingot
CN105954179A (en) * 2016-04-25 2016-09-21 中国石油天然气集团公司 Test method for measuring metallic material elemental sulfur stress corrosion cracking sensitivity

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050145311A1 (en) * 2003-12-30 2005-07-07 Walker Elizabeth L. Method for monitoring surface treatment of copper containing devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102116730A (en) * 2010-12-09 2011-07-06 中兴通讯股份有限公司 Method for testing porosity of electric connector gold-plating layer
CN102393427A (en) * 2011-11-02 2012-03-28 山西太钢不锈钢股份有限公司 Analyzing method of Ni content in melted steel ingot
CN105954179A (en) * 2016-04-25 2016-09-21 中国石油天然气集团公司 Test method for measuring metallic material elemental sulfur stress corrosion cracking sensitivity

Non-Patent Citations (1)

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化学镀镍磷合金镀层孔隙率的电化学评价;俞宏英, 孙冬柏, 黄锦滨, 杨德钧;电化学(第03期);全文 *

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