CN114775013A - Passivation solution for stainless steel plate (piece) and electrochemical passivation process thereof - Google Patents
Passivation solution for stainless steel plate (piece) and electrochemical passivation process thereof Download PDFInfo
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- CN114775013A CN114775013A CN202210221743.6A CN202210221743A CN114775013A CN 114775013 A CN114775013 A CN 114775013A CN 202210221743 A CN202210221743 A CN 202210221743A CN 114775013 A CN114775013 A CN 114775013A
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- 238000002161 passivation Methods 0.000 title claims abstract description 135
- 239000010935 stainless steel Substances 0.000 title claims abstract description 94
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000001978 electrochemical passivation Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 235000019830 sodium polyphosphate Nutrition 0.000 claims abstract description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 15
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 13
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 13
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000001509 sodium citrate Substances 0.000 claims abstract description 12
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 10
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 2
- 229960001484 edetic acid Drugs 0.000 claims 1
- 235000019794 sodium silicate Nutrition 0.000 claims 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 238000005536 corrosion prevention Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005498 polishing Methods 0.000 description 12
- 239000012459 cleaning agent Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229960002163 hydrogen peroxide Drugs 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000006388 chemical passivation reaction Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
Abstract
The invention belongs to the technical field of stainless steel corrosion prevention, and particularly relates to a stainless steel plate (piece) passivation solution and an electrochemical passivation process thereof. The passivation solution comprises a basic solute and a solvent, wherein the basic solute is sodium sulfate and one of sodium silicate or sodium polyphosphate, and the solvent is water. The passivation solution can also comprise an additive, wherein the additive is one or more of disodium ethylene diamine tetraacetate, sodium citrate, hydrogen peroxide or sodium molybdate. The passivation process adopting the method comprises the following steps: adding a passivation solution into an electrolytic tank, connecting the pretreated stainless steel plate (piece) to a double-pulse power supply anode, connecting the electrolytic tank to a power supply cathode, placing the stainless steel plate (piece) in the passivation solution, adjusting electrical parameters, and stirring the passivation solution in the electrolytic tank to passivate the stainless steel plate (piece). The passivation solution disclosed by the invention adopts environment-friendly components, the operating environment has no defects of acid gas and high temperature, the passivation solution can be repeatedly utilized, the waste liquid treatment cost is low, and the passivation solution is green and environment-friendly; the process has high passivation efficiency and good passivation effect.
Description
Technical Field
The invention belongs to the technical field of stainless steel corrosion prevention, and particularly relates to a stainless steel plate (piece) passivation solution and an electrochemical passivation process thereof.
Background
Stainless steel sheets (parts) are widely used in the fields of medical treatment, machinery, chemical industry, metallurgy, ships, and the like because of their excellent corrosion resistance. In some complex media, however, corrosion still inevitably occurs, thereby causing a large economic loss.
At present, the formulation of the passivation solution and the passivation process which are actually applied still have some problems.
(1) From the aspect of environmental protection, the passivation process of the stainless steel plate (piece) which is widely applied at present relates to strong acid or chromium-containing components, the operation environment is poor, the waste liquid has certain pollution to the environment, and the waste liquid treatment cost is high. Although environment-friendly acid passivation technology appears, the technology is not mature enough to be further improved, and cannot meet the requirement of practical application.
(2) From the passivation process, chemical passivation is a widely applied stainless steel plate (part) passivation method at present, the chemical passivation is simple and convenient to operate, but the passivation treatment time is relatively long, so that the further application of chemical passivation is restricted.
(3) From the passivation efficiency point of view, the passivation efficiency is still low, and the application and popularization are difficult to realize. The current electrochemical passivation time is generally over 30min, and the chemical passivation time is longer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the passivation solution for the stainless steel plate (piece), which adopts environment-friendly components, has no defects of acid gas and high temperature in the operation environment, can be repeatedly utilized, has low waste liquid treatment cost and is green and environment-friendly; the invention also provides an electrochemical passivation process adopting the electrochemical passivation solution, and the electrochemical passivation solution has high passivation efficiency and good passivation effect.
The purpose of the invention is realized by the following technical scheme:
the passivation solution for the stainless steel plate (piece) is an acid-free passivation solution and comprises a basic solute and a solvent, wherein the basic solute is sodium sulfate and one of sodium silicate or sodium polyphosphate, and the solvent is water.
Preferably, the stainless steel plate (piece) passivation solution further comprises an additive, wherein the additive is one or more of disodium ethylene diamine tetraacetate, sodium citrate, hydrogen peroxide or sodium molybdate.
The passivation solution comprises the following components in percentage by weight:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate;
0-15g/L of disodium ethylene diamine tetraacetate;
0-15g/L sodium citrate;
0-15 vol% of hydrogen peroxide;
0-15g/L of sodium molybdate.
The passivation solution mainly has the following preferred schemes:
the first scheme comprises the following steps:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate.
Scheme II:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate;
0.1-15g/L of disodium ethylene diamine tetraacetate.
And a third scheme is as follows:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate;
0.1-15g/L of sodium molybdate.
And the scheme is as follows:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate;
1-15 vol% of hydrogen peroxide.
And a fifth scheme:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate;
0.1-15g/L of sodium citrate;
1-15 vol% of hydrogen peroxide;
0.1-15g/L of sodium molybdate.
The five schemes are formulas of the passivation solution for the stainless steel plate (piece) with relatively good effect, but the invention is not limited to the formulas.
The preparation method of the passivation solution comprises the following steps:
firstly, dissolving basic solute components in a solvent, then adding an additive into the solvent for dissolving, and adopting a mechanical stirring and heating (lower than 40 ℃) mode to accelerate the dissolution in the dissolving process.
In the passivation solution of the present invention, the passivation solution,sodium silicate (sodium polyphosphate) and sodium sulfate mainly play a role in increasing the conductivity of the solution; in addition, the sodium silicate/sodium molybdate can play a certain corrosion inhibition role on the stainless steel plate (piece); the disodium ethylene diamine tetraacetate/sodium citrate mainly plays a complexing role and can complex Fe generated on the surface of a stainless steel plate (piece) in a passivation reaction3+And the reaction rate is accelerated. The oxydol can increase the oxidability of the passivation solution and accelerate the reaction rate. The passivating solution is alkalescent, the components of the passivating solution are all environment-friendly components, acid, chromium-containing substances and the like are not involved, the cyclic utilization rate of the passivating solution is high, and the treatment cost of waste liquid is low.
The electrochemical passivation process adopting the passivation solution for the stainless steel plate (piece) comprises the following steps: adding a passivation solution into an electrolytic tank, connecting the pretreated stainless steel plate (piece) to a double-pulse power supply anode, connecting the electrolytic tank to a power supply cathode, placing the stainless steel plate (piece) in the passivation solution, adjusting electrical parameters, and stirring the passivation solution in the electrolytic tank to passivate the stainless steel plate (piece). After the passivation treatment is finished, the stainless steel plate (piece) is washed by clean water (or airflow) and naturally (or artificially) dried.
Wherein:
the pretreatment is to polish the surface. The grinding and polishing are mechanical grinding and electrochemical (chemical) polishing, the surface is treated until no obvious scratch is formed, then the surface is respectively placed in a water-based oil removal cleaning solution for cleaning and rinsing in clear water, and finally the surface is dried to constant weight.
Grinding and polishing: the purpose is to remove the oxide skin on the surface of the stainless steel plate (piece) and simultaneously to flatten the surface of the stainless steel plate (piece) so as to prepare for passivation treatment.
Cleaning and washing: the degreasing cleaning solution can remove oil stains attached to the stainless steel plate (piece) in the grinding and polishing process, and deionized water is used for washing to further clean the surface of the stainless steel plate (piece).
The electrical parameter range is as follows: positive voltage is 20-200V, negative voltage is 1-20V, positive duty ratio is 20-50%, negative duty ratio is 20-50%, and frequency is 50-1000 Hz. By adopting a double-pulse power supply and adjusting parameters such as voltage, duty ratio, frequency and the like, the appearance and the density of the generated passive film can be regulated and controlled, and the passive film with good corrosion resistance is obtained.
The passivation time is 1-20 min. Compared with the common acid pickling passivation, the passivation efficiency is greatly improved.
The passivation treatment process controls the temperature of the passivation solution to be below 60 ℃.
And the temperature of the passivation solution is controlled in a physical cooling mode.
The physical cooling adopts the modes of electric refrigeration, low-temperature nitrogen introduction, low-temperature carbon dioxide introduction or water bath.
Compared with the prior art, the invention has the following beneficial effects:
1. the passivation solution disclosed by the invention is environment-friendly, does not contain acid, chromium and the like, has no defects of acid gas, high temperature and the like in an operation environment, can be recycled, is low in waste liquid treatment cost, does not pollute the environment, and accords with the environment-friendly idea.
2. The invention adopts the double-pulse power supply for passivation, can ensure that a passivation film with a certain thickness can be formed, and the thickness can reach the micron level and is far higher than the thickness of the traditional passivation film at the nanometer level. By adjusting the electrical parameters, the growth speed of the passive film can be controlled, the compactness of the passive film is increased, the surface of the passive film is smoother and smoother, and the decorative effect is good. According to the invention, voltage is applied to passivate the stainless steel plate (piece) in the environment of specific passivating liquid, and under the specific condition, the passivating time is shortened to be within 20min, so that the passivating efficiency is greatly improved. Compared with the common pickling passivation, the corrosion resistance of the stainless steel plate (piece) product is greatly improved. The corrosion resistance of the passivated stainless steel plate (piece) can be improved by several times.
Drawings
FIG. 1 is the surface topography of the comparative example 1 sample;
FIG. 2 is the surface topography of the comparative example 4 sample;
FIG. 3 is the surface topography of the sample of example 5;
FIG. 4 is the surface topography of the sample of example 15;
FIG. 5 is the cross-sectional profile of the sample of example 15;
FIG. 6 is the cross-sectional profile of the sample of example 16;
FIG. 7 is the surface relief of the sample of comparative example 1;
FIG. 8 is the surface relief of the sample of comparative example 3;
FIG. 9 is the surface relief of the sample of comparative example 4;
FIG. 10 is the surface relief of the sample of example 15;
FIG. 11 is a graph of a sample of comparative example 1;
FIG. 12 is a sample view of example 15;
fig. 13 is a graph of a sample of comparative example 4.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby. The procedures, conditions, reagents, test methods, and the like, which are carried out according to the present invention, are general knowledge and common general knowledge in the art, except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
The electrochemical passivation process adopting the passivation solution for the stainless steel plate (piece) is carried out according to the following steps:
(1) surface preparation
Firstly, mechanically polishing a stainless steel plate (piece), sequentially polishing the stainless steel plate (piece) by 400 meshes of abrasive paper, 600 meshes of abrasive paper and 800 meshes of abrasive paper to 3000 meshes of abrasive paper until no obvious scratch is left on the surface of the stainless steel plate (piece), then respectively placing the stainless steel plate (piece) in a water-based degreasing cleaning solution (a commercially available stainless steel cleaning agent and a Hill water-based cleaning agent) and clean water for cleaning, and finally drying to constant weight.
(2) Preparation of passivation solution
Dissolving basic solute in solvent under mechanical stirring and heating (below 40 deg.C) to accelerate dissolution. Pouring the prepared passivation solution into an electrolytic bath. The passivation solution comprises the following components in percentage by weight: sodium silicate 20g/L, sodium sulfate 1 g/L.
(3) Passivation treatment
Connecting the stainless steel plate (piece) obtained in the step (1) to a double-pulse power supply anode, connecting an electrolytic cell to a power supply cathode, then adjusting to specific electrical parameters, cooling the passivation solution (below 60 ℃) by using a water bath in the passivation process, and carrying out passivation treatment for 20 min. The specific electrical parameters are: the voltage is 200V positive, 1V negative, the positive duty ratio is 20%, the negative duty ratio is 30%, and the frequency is 50 Hz.
(4) Cleaning and drying
After the passivation treatment is finished, the stainless steel plate (piece) is washed by clear water and is placed and dried.
Example 2
The electrochemical passivation process adopting the passivation solution for the stainless steel plate (piece) is carried out according to the following steps:
(1) surface preparation
Firstly, mechanically polishing a stainless steel plate (piece), sequentially polishing the stainless steel plate (piece) by 400-mesh, 600-mesh and 800-mesh till 3000-mesh abrasive paper until the surface of the stainless steel plate (piece) has no obvious scratch, then respectively placing the stainless steel plate (piece) in a water-based oil removal cleaning solution (a commercially available stainless steel cleaning agent and a Hill water-based cleaning agent) and clear water for cleaning, and finally drying to constant weight.
(2) Preparation of passivation solution
Dissolving basic solute in solvent under mechanical stirring and heating (below 40 deg.C) to accelerate dissolution. Pouring the prepared passivation solution into an electrolytic bath. The passivation solution comprises the following components in percentage by weight: 1g/L of sodium silicate and 20g/L of sodium sulfate.
(3) Passivation treatment
Connecting the stainless steel plate (piece) obtained in the step (1) to a double-pulse power supply anode, connecting an electrolytic cell to a power supply cathode, then adjusting to specific electrical parameters, cooling the passivation solution (below 60 ℃) by using a water bath in the passivation process, and carrying out passivation treatment for 20 min. The specific electrical parameters are: positive voltage 20V, negative voltage 20V, positive duty cycle 50%, negative duty cycle 20%, frequency 1000 Hz.
(4) Cleaning and drying
After the passivation treatment is finished, the stainless steel plate (piece) is washed by clear water and is placed and dried.
Example 3
The difference from example 1 is that the passivation time is 10 min.
Example 4
The difference from example 1 is that the passivation time is 1 min.
Example 5
The electrochemical passivation process adopting the passivation solution for the stainless steel plate (piece) is carried out according to the following steps:
(1) surface preparation
Firstly, mechanically polishing a stainless steel plate (piece), sequentially polishing the stainless steel plate (piece) by 400 meshes of abrasive paper, 600 meshes of abrasive paper and 800 meshes of abrasive paper to 3000 meshes of abrasive paper until no obvious scratch is left on the surface of the stainless steel plate (piece), then respectively placing the stainless steel plate (piece) in a water-based degreasing cleaning solution (a commercially available stainless steel cleaning agent and a Hill water-based cleaning agent) and clean water for cleaning, and finally drying to constant weight.
(2) Preparation of passivation solution
Dissolving basic solute in a solvent, wherein the dissolution is accelerated by adopting a mechanical stirring and heating (lower than 40 ℃) mode in the dissolving process. Pouring the prepared passivation solution into an electrolytic bath. The passivation solution comprises the following components in percentage by weight: 10g/L of sodium silicate and 10g/L of sodium sulfate.
(3) Passivation treatment
Connecting the stainless steel plate (piece) obtained in the step (1) to a double-pulse power supply anode, connecting an electrolytic cell to a power supply cathode, then adjusting to specific electrical parameters, and cooling the passivation solution (below 60 ℃) by using a water bath in the passivation process for 10 min. The specific electrical parameters are: the voltage is 110V positive, 10V negative, 35% positive duty cycle, 35% negative duty cycle and 500Hz frequency.
(4) Cleaning and drying
After the passivation treatment is finished, the stainless steel plate (piece) is washed by clear water and placed and dried.
Example 6
The difference from the embodiment 5 is that the passivating solution also contains 0.1g/L of disodium ethylene diamine tetraacetate and 15g/L of sodium citrate.
Example 7
The difference from the embodiment 5 is that the passivating solution also contains 15g/L of disodium ethylene diamine tetraacetate and 0.1g/L of sodium citrate.
Example 8
The difference from the embodiment 5 is that the passivating solution also contains 7g/L of disodium ethylene diamine tetraacetate and 8g/L of sodium citrate.
Example 9
The difference from the embodiment 5 is that the passivating solution also contains 0.1g/L of sodium molybdate.
Example 10
The difference from the embodiment 5 is that the passivating solution also contains 15g/L of sodium molybdate.
Example 11
The difference from the embodiment 5 is that the passivating solution also contains 7g/L of sodium molybdate.
Example 12
The difference from the embodiment 5 is that the passivation solution also contains 1 vol% of hydrogen peroxide.
Example 13
The difference from the embodiment 5 is that the passivation solution also contains 15 vol% of hydrogen peroxide.
Example 14
The difference from the embodiment 5 is that the passivation solution also contains 7 vol% of hydrogen peroxide.
Example 15
The electrochemical passivation process adopting the passivation solution for the stainless steel plate (piece) is carried out according to the following steps:
(1) surface preparation
Firstly, mechanically polishing a stainless steel plate (piece), sequentially polishing the stainless steel plate (piece) by 400 meshes of abrasive paper, 600 meshes of abrasive paper and 800 meshes of abrasive paper to 3000 meshes of abrasive paper until no obvious scratch is left on the surface of the stainless steel plate (piece), then respectively placing the stainless steel plate (piece) in a water-based degreasing cleaning solution (a commercially available stainless steel cleaning agent and a Hill water-based cleaning agent) and clean water for cleaning, and finally drying to constant weight.
(2) Preparation of passivation solution
Firstly dissolving a basic solute in a solvent, then adding an additive into the solvent for dissolving, and adopting a mechanical stirring and heating (lower than 40 ℃) mode to accelerate the dissolution in the dissolving process. Pouring the prepared passivation solution into an electrolytic bath. The passivation solution comprises the following components in percentage by weight: 10g/L of sodium silicate, 8g/L of sodium sulfate, 8g/L of sodium citrate, 7 vol% of hydrogen peroxide and 3g/L of sodium molybdate.
(3) Passivation treatment
Connecting the stainless steel plate (piece) obtained in the step (1) to a double-pulse power supply anode, connecting an electrolytic cell to a power supply cathode, then adjusting to specific electrical parameters, cooling the passivation solution (below 60 ℃) by using a water bath in the passivation process, and carrying out passivation treatment for 10 min. The specific electrical parameters are: the voltage is 100V in positive direction, 8V in negative direction, 50% in positive duty ratio, 30% in negative duty ratio and 400Hz in frequency.
(4) Cleaning and drying
After the passivation treatment is finished, the stainless steel plate (piece) is washed by clear water and is placed and dried.
Example 16
The difference from example 15 is that the sodium silicate component in the passivation solution was replaced with sodium polyphosphate, and the concentration was still 10 g/L.
Comparative example 1
The stainless steel plate (piece) is only subjected to cleaning and drying treatment.
Comparative example 2
The difference from example 1 is that the stainless steel plate (piece) is not pretreated (ground and polished), and is directly cleaned and dried and then passivated.
Comparative example 3
The difference from example 1 is that the stainless steel sheet (piece) was subjected to only pretreatment and was not subjected to passivation treatment.
Comparative example 4
The pickling and passivating treatment process for the stainless steel plate (piece) is carried out according to the following steps:
(1) pretreatment of
Firstly, the stainless steel plate (piece) is put into degreasing cleaning solution (commercial stainless steel cleaning agent, Hill water-based cleaning agent) for cleaning, then the stainless steel plate (piece) is washed by clean water and dried to constant weight.
(2) Preparation of passivation solution
Preparing passivation solution, and pouring the passivation solution into a passivation pool. The passivation solution comprises the following specific components in percentage by weight: 20 wt.% nitric acid, 10 wt.% hydrofluoric acid and 70 wt.% water.
(3) Passivation treatment
And (3) soaking the stainless steel plate (piece) treated in the step (1) into the passivation solution prepared in the step (2), and keeping the temperature for 50min at normal temperature.
(4) Cleaning and drying
After the passivation treatment is finished, the stainless steel plate (piece) is washed by clear water and is placed and dried.
And (3) testing:
using 304 stainless steel plates as the test subjects, the plates of 304 stainless steel plates were cut into stainless steel samples of 25 mm. times.10 mm. times.3 mm, randomly divided into 20 groups, and treated according to the procedures of examples 1 to 16 and comparative examples 1 to 4 above, using WHD-30 power supply equipment designed and manufactured by the institute of Harbin Industrial university. And (3) carrying out corrosion resistance test on the sample by combining GB/T24196-2009 constant potential and potentiodynamic polarization measurement guide rule of metal and alloy corrosion electrochemical test method. And (3) wax sealing treatment is carried out on the sample, the sample is placed in 3.5% sodium chloride solution, a polarization curve test is carried out by adopting an electrochemical workstation CHI 660E, and the self-corrosion potential and the self-corrosion current density are obtained after fitting as shown in the table 1. The thickness of the passivation film is measured by adopting a method of inlaying a sample, grinding and polishing the observation section. The thickness of the passivation film of the acid-washed stainless steel of comparative example 4 is in the nanometer level and cannot be measured by a section observation method.
TABLE 1304 Corrosion resistance data for stainless steel coupons
According to the stainless steel corrosion resistance evaluation rule: (1) the more positive the self-etching potential, the smaller the etching tendency; (2) the smaller the self-corrosion current density is, the slower the corrosion speed is; (3) the more positive the self-corrosion potential and the smaller the self-corrosion current density, the better the corrosion resistance.
From table 1, it can be seen that:
1. comparing the data of the example 1 and the comparative examples 1 to 3, the pretreatment can greatly reduce the corrosion resistance tendency of the stainless steel, the passivation treatment can greatly reduce the corrosion rate of the stainless steel, and the combination of the pretreatment and the passivation can improve the corrosion resistance of the passivated stainless steel.
2. The comparison of the data of the embodiment 5 and the embodiments 1 to 4 can obtain that the proper component concentration, the electrical parameter range and the reasonable passivation time of the passivation solution are more beneficial to obtaining good stainless steel passivation effect.
3. Comparing the data of example 5 with those of examples 6 to 8, examples 9 to 11, and examples 12 to 14, it can be seen that the corrosion resistance of the passivated stainless steel can be greatly improved by adding appropriate amounts of disodium ethylenediaminetetraacetate, sodium citrate, sodium molybdate, and hydrogen peroxide.
4. Comparison of the data from example 15 and example 16 shows that sodium polyphosphate can replace sodium silicate as the basic passivation solution component and that sodium polyphosphate is relatively inexpensive. However, the passivation effect using sodium polyphosphate is not as good as that using sodium silicate. The selection of the two is to make final judgment according to the corrosion resistance requirement of the product by comprehensively considering the cost and the passivation effect.
5. Comparing the data of example 15 with the data of comparative example 4, the electrochemical passivation method of stainless steel of the present invention has better passivation effect and higher efficiency compared with the traditional pickling passivation method, and better conforms to the current environmental protection concept.
Claims (10)
1. The passivation solution for the stainless steel plate (piece) is characterized in that: the solute comprises basic solute and solvent, wherein the basic solute is sodium silicate or sodium polyphosphate or sodium sulfate, and the solvent is water.
2. The passivation solution for stainless steel plates (pieces) according to claim 1, characterized in that: the additive is one or more of ethylene diamine tetraacetic acid, sodium citrate, hydrogen peroxide or sodium molybdate.
3. The passivation solution for stainless steel plates (pieces) according to claim 2, characterized in that: the content of each component in the passivation solution is as follows:
1-20g/L of sodium silicate or sodium polyphosphate;
1-20g/L of sodium sulfate;
0-15g/L of disodium ethylene diamine tetraacetate;
0-15g/L sodium citrate;
0-15 vol% of hydrogen peroxide;
0-15g/L of sodium molybdate.
4. An electrochemical passivation process using the passivation solution for stainless steel plates (members) according to any of claims 1 to 3, characterized in that: the method comprises the following steps: adding a passivation solution into an electrolytic tank, connecting the pretreated stainless steel plate (piece) to a double-pulse power supply anode, connecting the electrolytic tank to a power supply cathode, placing the stainless steel plate (piece) in the passivation solution, adjusting electrical parameters, and stirring the passivation solution in the electrolytic tank to passivate the stainless steel plate (piece).
5. The electrochemical passivation process of the passivation solution for stainless steel plates (pieces) according to claim 4, characterized in that: the pretreatment is to polish and polish the surface.
6. The electrochemical passivation process of the passivation solution for stainless steel plates (pieces) of claim 4, characterized in that: the electrical parameter ranges are: positive voltage 20-200V, negative voltage 1-20V, positive duty ratio 20-50%, negative duty ratio 20-50%, and frequency 50-1000 Hz.
7. The electrochemical passivation process of the passivation solution for stainless steel plates (pieces) according to claim 4, characterized in that: the passivation time is 1-20 min.
8. The electrochemical passivation process of the passivation solution for stainless steel plates (pieces) according to claim 4, characterized in that: the temperature of the passivation solution is controlled below 60 ℃ in the passivation treatment process.
9. The electrochemical passivation process of stainless steel plate passivation solution of claim 8, characterized in that: the temperature of the passivation solution is controlled in a physical cooling mode.
10. The electrochemical passivation process of stainless steel plate passivation solution of claim 9, characterized in that: the physical cooling adopts the modes of electric refrigeration, low-temperature nitrogen introduction, low-temperature carbon dioxide introduction or water bath.
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