CN103806083A - Alkaline-electrolysis rust removal method - Google Patents

Alkaline-electrolysis rust removal method Download PDF

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Publication number
CN103806083A
CN103806083A CN201310540644.5A CN201310540644A CN103806083A CN 103806083 A CN103806083 A CN 103806083A CN 201310540644 A CN201310540644 A CN 201310540644A CN 103806083 A CN103806083 A CN 103806083A
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electrolysis
alkaline
scale
derusting
electrolysis treatment
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Inventor
程一麟
白育纶
赖政隆
何家敬
曾婉宁
白家祥
栗爱纲
李世文
许雯婷
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ZEN MATERIAL TECHNOLOGIES Inc
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ZEN MATERIAL TECHNOLOGIES Inc
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Abstract

The invention provides an alkaline-electrolysis rust removal method. The method comprises the steps of (A) providing a steel material covered with rust scale, (B) taking the steel material covered with the rust scale as an anode, putting the steel material in an alkaline electrolyte containing tartrate for alkaline electrolysis treatment, and then obtaining the electrolyzed steel material, and (C) providing a mechanical force for the electrolyzed steel material until the rust scale is separated from the surface of the steel material and then obtaining the steel material without being covered with the rust scale, wherein the concentration of the electrolyte is greater than or equal to 0.4M, and the current density of the electrolysis is greater than or equal to 10A/dm<2>. The alkaline-electrolysis rust removal method does not need multiple times of electrolysis treatment, and thus meets the requirement for environmental protection while guaranteeing the economic benefit.

Description

Alkaline electrolysis derusting method
Technical field
The present invention has about a kind of alkaline electrolysis derusting method, refers to that especially a kind of steel that contain scale via effects on surface carry out the derusting method of alkaline electrolysis processing, belong to steel field of smelting.
Background technology
Steel (as stainless steel) are in high-temperature technology (as hot rolling or annealing or other thermal treatment etc.), and surface may generate one deck black scale, and its main component is the metal oxides such as ferric oxide, nickel oxide and chromic oxide.This black scale not only affects the outward appearance of steel, also has impact for following process, therefore, conventionally can comprise the step of a removal scale in the process of making steel.
Conventional removal scale mode is pickling, in addition, for the scale of more difficult removal, also needs to utilize some auxiliary treatment (as salt bath processing, electrolytic derusting or additional mechanical force) to improve rust cleaning efficiency.The acid solution that pickling is used comprises sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid etc., in the time of practice, easily there is pickling not exclusively or the problem such as over-pickling, and the difference of pickling degree also can have a strong impact on stainless outward appearance, for example stainless steel surface produces most holes and unsmooth light.Except the problems referred to above, a large amount of spent pickle liquors that acid cleaning process produces are because containing the heavy metals such as iron, chromium, nickel, need carry out special processing and just can under environmental protection demand, discharge waste liquid meeting, and acid solution also may produce oxynitride (as NO, NO 2) etc. air pollutant.
U.S. Patent Bulletin the 5th, 897, disclose for No. 764 a kind ofly for removing the method for surface scale of high-grade steel band, comprised (1) electrolysis treatment: utilize ammonium sulfate, sodium sulfate, sulfuric acid etc. as electrolytic solution, and (2) ultrasound clean.This patent is used acidic electrolysis mode instead, though can reduce the usage quantity of acid solution, after acidic electrolysis, will make to exist heavy metal ion, this heavy metal ion to be difficult for reclaiming in acid electrolyte, and in order to meet environmental protection demand, will improve treatment cost of waste liquor.
From the above, for meeting under economic benefit and environmental protection demand, effectively remove the scale of steel surface, and obtain the steel of surface smoothing light simultaneously, still have the great space of improving.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide one not need to use acid solution, meet the alkaline electrolysis derusting method of economic benefit and environmental protection demand simultaneously.
For reaching above-mentioned purpose, the invention provides a kind of alkaline electrolysis derusting method, it comprises following steps:
(A) steel that, provide a surface to contain scale;
(B), make steel that described surface contains scale as anode, then insert in an alkaline electrolyte that contains tartrate and carry out alkaline electrolysis processing, this concentration of electrolyte is more than or equal to 0.4M, and the current density of electrolysis is more than or equal to 10A/dm 2, to obtain the steel through electrolysis treatment; And
(C), provide a mechanical force to the described steel through electrolysis treatment, until scale depart from from the surface of these steel and make the steel of a surface without scale.
Alkaline electrolysis derusting method of the present invention uses the alkaline electrolyte that contains tartrate to carry out electrolysis treatment, and the mechanical treatment of arranging in pairs or groups, and can obtain the steel of surface smoothing light.Method of the present invention is without electrolysis treatment repeatedly and meet economic benefit, and the electrolysis treatment of method of the present invention is alkaline electrolysis, do not use acid electrolyte, thereby there is no the emission problem of spent pickle liquor; Moreover, after alkaline electrolysis, can allow scale reduction produce metal ion and generate metal oxide or metal hydroxides with basic group, and metal hydroxides will be deposited in electrolyzer bottom, follow-uply only need to be recyclable alkaline electrolyte, to meet environmental protection demand completely metal hydroxides filtering.In addition, it is worth mentioning that, method of the present invention, in the time that alkaline electrolysis is processed, will be removed the grease of steel surface simultaneously, and is omitted degrease flow process (conventionally comprising alkali cleaning, cleaning and three steps of acid neutralization).
Below will be elaborated with regard to content of the present invention:
In aforesaid method, the steel that scale is contained on the surface in step (A) can be any by hot rolling or other thermal treatment and formed the steel of one deck black scale in surface.
This any surface of steel general reference can form the steel of scale.Preferably, these steel are to be selected from stainless steel, carbon steel or steel alloy.In specific embodiments of the invention, these steel are stainless steel.
In aforesaid method, preferably, the tartrate in step (B) is one or more the combination being selected from sodium tartrate, soluble tartrate and sodium-potassium tartrate.In a specific embodiment of the present invention, this tartrate is sodium tartrate.
In aforesaid method, step (B) be there is scale using described surface steel as anode, described in contain tartrate alkaline electrolyte as electrolytic solution, and install according to general electrolyzer.In addition, except the steel that have scale using surface are as anode, the steel that its surface in wish processing has a scale also can be positioned over responds to alkaline electrolysis in alkaline electrolyte, and can effectively remove scale.
In alkaline electrolyte in step (B), need special one to carry, tartrate, particularly sodium tartrate, only for copper-plating technique or as antioxidant, acid adjusting agent or emulsifying agent, be never used in the electrolytic solution as derusting process in the past.Electrolysis treatment in step (B) is mainly that the tartrate ion that dissociates out by this tartrate reacts with scale, to allow scale structure be damaged and to become loose, and is beneficial to the removal of follow-up scale.
In aforesaid method, preferably, the electrolysis treatment in step (B) is to carry out under 7 to 8.5 pH value scope.More preferably, the electrolysis treatment in step (B) is to carry out under 7.5 to 8.5 pH value scope.In specific embodiments of the invention, this pH value scope is 7.8 to 8.
In aforesaid method, in the alkaline electrolyte that contains tartrate in step (B), selectively add any conventional additive, such as interfacial agent, metal chelator etc.Preferably, the alkaline electrolyte that contains tartrate in step (B) is the sodium tartrate aqueous solution.More preferably, the concentration range of this sodium tartrate aqueous solution is 0.8 to 1.0M.
In aforesaid method, preferably, the current density range of the electrolysis treatment in step (B) is 20 to 160A/dm 2, when current density is lower than 20A/dm 2time, scale there is no crack performance; And when current density is higher than 160A/dm 2time, not only need to expend compared with multiple-energy-source and electrolyzer and may damage because of overheated.More preferably, this current density range is 20 to 100A/dm 2; Particularly preferably, this current density range is 40 to 100A/dm 2; Particularly preferably, this current density range is 60 to 100A/dm 2.
In aforesaid method, preferably, step (B) is to carry out under the temperature range of 30 to 70 ℃.More preferably, this temperature range is 60 to 70 ℃.
In aforesaid method, preferably, the electrolysis treatment time range in step (B) is 60 to 300 seconds.In a specific embodiment of the present invention, this electrolysis treatment time is 120 seconds.
According to the specific embodiment of the present invention, preferably, above-mentioned alkaline electrolysis derusting method more comprises one in step (B) step (B1) afterwards, this step (B1) is to make the described steel through electrolysis treatment as anode, insert again in an alkaline electrolyte that contains tertiary sodium phosphate and carry out electrolysis treatment for the second time, to obtain through the steel of electrolysis treatment for the second time.
In aforesaid method, step (B1) is using the described steel through electrolysis treatment as anode, described in contain tertiary sodium phosphate alkaline electrolyte as electrolytic solution, and install according to general electrolyzer.Phosphate anion that the surface scale of the described steel through electrolysis treatment can dissociate with tertiary sodium phosphate produces and react, and phosphate radical phosphorus also can react through scale and with steel surface generation, and allows scale be removed and make steel surface to present cloudy surface state.
In aforesaid method, preferably, the electrolysis treatment for the second time in step (B1) is to carry out under 8 to 13 pH value scope.
In aforesaid method, preferably, the alkaline electrolyte that contains tertiary sodium phosphate in step (B1) is trisodium phosphate aqueous solution.More preferably, the concentration range of this trisodium phosphate aqueous solution is 0.2 to 0.6M.
In aforesaid method, in the alkaline electrolyte that contains tertiary sodium phosphate in step (B1), selectively add any conventional additive, such as interfacial agent, metal chelator etc.Preferably, in this alkaline electrolyte that contains tertiary sodium phosphate, more contain a metal chelator, this metal chelator is one or more the combination being selected from citric acid, sodium-chlor, oxalic acid, propanedioic acid and nitric acid.More preferably, this metal chelator is to be selected from citric acid, sodium-chlor or both combinations.The addition of this metal chelator can be adjusted according to actual needs, and preferably, take tertiary sodium phosphate weight as 100 listed as parts by weight, the addition scope of metal chelator is 10 to 25 weight parts.
In aforesaid method, preferably, the current density range of the electrolysis treatment for the second time in step (B1) is 20 to 160A/dm 2, when current density is lower than 20A/dm 2time, scale is remained stationary; And when current density is higher than 160A/dm 2time, not only need to expend compared with multiple-energy-source and electrolyzer and may damage because of overheated.More preferably, this current density range is 20 to 100A/dm 2; Particularly preferably, this current density range is 40 to 100A/dm 2; Particularly preferably, this current density range is 60 to 100A/dm 2.
In aforesaid method, preferably, step (B1) is to carry out under the temperature range of 30 to 70 ℃.More preferably, this temperature range is 60 to 70 ℃.
In aforesaid method, preferably, the time range of electrolysis treatment for the second time in step (B1) is 60 to 180 seconds.In a specific embodiment of the present invention, this electrolysis treatment time is 60 seconds.
In aforesaid method, preferably, in the alkaline electrolyte in step (B), more contain polyoxyethylene glycol.In the time more containing polyoxyethylene glycol in alkaline electrolyte, can reduce the surface tension of water, increase adsorption activity and make electrolytic solution more can be attached to steel surface, and make electrolytic process more smooth.
In aforesaid method, preferably, the mechanical force in step (C) is provided by the mode of following formed group: the combination of one or more in brushing, wiping and ultrasonic vibrating.More preferably, the mechanical force in step (C) is provided by the mode of following formed group: brushing, ultrasonic vibrating and both combinations.Particularly preferably, the mechanical force in step (C) is provided by brushing and ultrasonic vibrating.
Via the prepared surface of method of the present invention without the steel of scale without passing through again any surface treatment (as polishing), can allow steel there is level and smooth and bright surface, and meet the required outward appearance of industry completely.In addition, for example, as wished different steel outward appearances (cloudy surface) because of follow-up user demand, the step (B1) that can arrange in pairs or groups in the inventive method.
Accompanying drawing explanation
Fig. 1 is the steps flow chart schematic diagram of a specific embodiment of the inventive method;
Fig. 2 is the SEM photo of the stainless steel wire through electrolysis treatment of embodiment 2, and current density is 60A/dm 2;
Fig. 3 is the SEM photo of the stainless steel wire through electrolysis treatment of embodiment 3, and current density is 80A/dm 2;
Fig. 4 is the SEM photo of the stainless steel wire through electrolysis treatment of embodiment 4, and current density is 100A/dm 2;
Fig. 5 is the SEM photo of the stainless steel wire without electrolysis treatment of comparative example 3;
Fig. 6 is that the EDS of the stainless steel materials without electrolytic derusting processing of embodiment 19 analyzes photo;
Fig. 7 be embodiment 19 without the each composition ratio distribution plan on the stainless steel materials of electrolytic derusting processing;
Fig. 8 is that the EDS of the stainless steel materials through electrolytic derusting processing of embodiment 19 analyzes photo;
Fig. 9 is the each composition ratio distribution plan on the stainless steel materials of electrolytic derusting processing of embodiment 19;
Figure 10 be embodiment 19 through the SEM photo of the stainless steel wire of electrolysis treatment for the first time, current density is 20A/dm 2;
Figure 11 be embodiment 20 through the SEM photo of the stainless steel wire of electrolysis treatment for the first time, current density is 40A/dm 2;
Figure 12 be embodiment 21 through the SEM photo of the stainless steel wire of electrolysis treatment for the first time, current density is 60A/dm 2;
Figure 13 be embodiment 22 through the SEM photo of the stainless steel wire of electrolysis treatment for the first time, current density is 80A/dm 2;
Figure 14 be embodiment 23 through the SEM photo of the stainless steel wire of electrolysis treatment for the first time, current density is 100A/dm 2;
Figure 15 is the SEM photo of the stainless steel wire without electrolysis treatment of comparative example 7.
Primary clustering nomenclature:
The steel that scale is contained on 1 surface
2 alkaline electrolytes that contain tartrate
3 steel through electrolysis treatment
4 mechanical forces
5 surfaces are without the steel of scale
Embodiment
In a specific embodiment of the present invention, the steps flow chart of this alkaline electrolysis derusting method as shown in Figure 1, comprises: (A), the steel 1 that provide a surface to contain scale; (B), make steel 1 that this surface contains scale as anode, insert again in an alkaline electrolyte that contains tartrate 2 and carry out alkaline electrolysis processing, alkaline electrolyte 2 concentration that this contains tartrate are more than or equal to 0.4M, and the current density of electrolysis is more than or equal to 10A/dm 2, to obtain the steel 3 through electrolysis treatment; And (C), provide a mechanical force 4 to these steel 3 through electrolysis treatment, until scale departs from from the surface of these steel and makes the steel 5 of a surface without scale.
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
First get the stainless steel wire that a surface has black scale (purchased from Hua Xin stainless steel company, model is SS316, and the diameter of stainless steel wire is 5.5mm, and length is 50mm, scale thickness be 20 μ m).Again using this stainless steel wire as anode, and to put into concentration be that the sodium tartrate aqueous solution of 0.5M is (as electrolytic solution, to allocate and make by sodium tartrate and water, pH value is 7.8) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain an electrolyzer.By adjusting this power supply unit, make the current density of this electrolyzer be controlled at 40A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this stainless steel wire carries out alkaline electrolysis processing.
, after 120 seconds, take out this through the stainless steel wire of electrolysis treatment and be positioned in a ultrasonic vibrating device and shake until electrolysis treatment, lasting after 60 seconds, then carry out brushing with cloth (3M company manufactures, and model is 8501), make one bright stainless steel.
Outward appearance is observed
By the outward appearance of visual inspection embodiment 1 prepared stainless steel, result is as shown in table 1 below.
Comparative example 1 and 2
Comparative example 1 and 2 is to carry out electrolytic derusting according to the same steps flow process of embodiment 1, utilizes same steps to carry out outward appearance observation simultaneously, and difference is: comparative example 1 is that sodium citrate aqueous solution using 0.5M is as electrolytic solution; Comparative example 2 is that aqueous sodium hydroxide solution using 0.5M is as electrolytic solution.Test result arranges respectively in following table 1.
Table 1
Figure BDA0000407680160000061
Interpretation of result: as shown in Table 1, the scale removal effect of embodiment 1 is best, proves to use the sodium tartrate aqueous solution can effectively remove most scale as electrolytic solution.
Embodiment 2 to 4
First get the stainless steel wire that a surface has black scale (purchased from Hua Xin stainless steel company, model is SS316, and the diameter of stainless steel wire is 5.5mm, and length is 50mm, scale thickness be 20 μ m).Again using this stainless steel wire as anode, and to put into concentration be that the sodium tartrate aqueous solution of 0.5M is (as electrolytic solution, to allocate and make by sodium tartrate and water, pH value is 7.8 to 8) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain an electrolyzer.By adjusting this power supply unit, make that the current density of this electrolyzer is controlled at 60,80,100A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this stainless steel wire carries out alkaline electrolysis processing.
Until electrolysis treatment after 120 seconds, take out this stainless steel wire through electrolysis treatment and utilize and be serially connected with energy dispersion x-ray spectrometer (energy dispersive X-ray spectroscopy, EDS) sweep electron microscope (SEM) is observed the scale be full of cracks degree after electrolysis treatment, and sample in the time amplifying 40 times, the simultaneously composition of test surfaces scale, outward appearance photo as shown in Fig. 2, Fig. 3, Fig. 4 (can find out scale be full of cracks degree by Fig. 2 to 4) and test result as shown in table 2 below.
The stainless steel wire testing is positioned in a ultrasonic vibrating device and is shaken, lasting after 60 seconds, then carry out brushing with cloth (3M company manufactures, and model is 8501), make one bright stainless steel.
Outward appearance is observed
By the outward appearance of visual inspection embodiment 2 to 4 prepared stainless steels, result is as shown in table 2 below.
Comparative example 3
Get stainless steel wire that a surface has black scale (purchased from Hua Xin stainless steel company, model is SS316, the diameter of stainless steel wire is 5.5mm, length is 50mm, scale thickness be 20 μ m), recycling is serially connected with energy dispersion x-ray spectrometer (energy dispersive X-ray spectroscopy, EDS) sweep electron microscope (SEM) is observed the outward appearance without electrolysis treatment, and sample in the time amplifying 40 times, the simultaneously composition of test surfaces scale, outward appearance photo as shown in Figure 5 and test result as shown in table 2 below.
Table 2
Figure BDA0000407680160000071
Figure BDA0000407680160000081
Interpretation of result: the result by Fig. 2 to Fig. 5 can be found, when current density is 60A/dm 2when above, there is obvious crack performance through the scale on the stainless steel wire surface of electrolysis treatment, be conducive to shorten the treatment time of follow-up ultrasonic vibrating and brushing.As shown in Table 2, when current density is 60A/dm 2when above, the content of oxygen is obviously reduced to 5.44 by 48.4, represents that the content of oxide compound reduces, and also proves that working as current density is 60A/dm simultaneously 2when above, rust cleaning efficiency is better.
Embodiment 5 to 11
Embodiment 5 to 11 carries out electrolytic derusting according to the same steps flow process of embodiment 1, utilizes same steps to carry out outward appearance observation simultaneously, and difference is: concentration of electrolyte and the current density of embodiment 5 and 6 are different from embodiment 1; Concentration of electrolyte, current density and the temperature of embodiment 7 to 11 are different from embodiment 1.Electrolysis treatment condition and test result arrange respectively in following table 3.
In addition, utilize following flow process assessment scale to remove degree: utilize hundred lattice scale computing methods to assess scale and remove degree, result is as shown in table 3 below.When scale degree is A, represent that rust cleaning rate is 95%; When scale degree is B, represent that rust cleaning rate is 90%; When scale degree is C, represent that rust cleaning rate is 85%; When scale degree is D, represent that rust cleaning rate is 80%.The acceptable rust cleaning rate of industry is more than 90% at present, and namely scale degree is required to be A or B.
Comparative example 4
Comparative example 4 is to carry out electrolytic derusting according to the same steps flow process of embodiment 1, and difference is: the concentration of electrolyte of comparative example 4 and current density are different from embodiment 1.Electrolysis treatment condition and the test result of above-mentioned each comparative example refer to following table 3.
Table 3
Figure BDA0000407680160000082
Figure BDA0000407680160000091
Interpretation of result: the result by table 3 can find, the scale of embodiment 5 to 11 is removed degree can meet industry demand, and the surface of prepared stainless steel is level and smooth and bright really.Wherein remove degree the best with the scale of embodiment 10 and 11.What is particularly worth mentioning is that, the above results also confirms simultaneously: method of the present invention only needs to use single electrolytic solution (containing the alkaline electrolyte of sodium tartrate), then the mechanical force processing of arranging in pairs or groups, and just can effectively remove scale.
Embodiment 12 to 17
First get the different steel wires (as shown in table 4) that surface has black scale, length is 50mm, and scale thickness is 20 μ m.Again using this steel wire as anode, and to put into concentration be that the sodium tartrate aqueous solution of 0.5M is (as electrolytic solution, to allocate and make by sodium tartrate and water, pH value is 7.8 to 8) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain an electrolyzer.By adjusting this power supply unit, make the current density of this electrolyzer be controlled at 20A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this steel wire carries out electrolysis treatment.
After electrolysis treatment, the steel wire of handling is positioned in a ultrasonic vibrating device and is shaken, lasting after 60 seconds, then carrying out brushing with cloth (3M company manufactures, and model is 8501), make one bright steel, test result is as shown in table 4 below.
Outward appearance is observed
By the outward appearance of visual inspection embodiment 12 to 17 prepared steel, result is as shown in table 4 below.
Table 4
Figure BDA0000407680160000092
Figure BDA0000407680160000101
Interpretation of result: proved by table 4, method of the present invention is applicable to process different steel, and can effectively remove the scale of steel surface.
Embodiment 18
First get the stainless steel wire that a surface has black scale (purchased from Hua Xin stainless steel company, model is SS316, and the diameter of stainless steel wire is 5.5mm, and length is 50mm, scale thickness be 20 μ m).Again using this stainless steel wire as anode, and to put into concentration be that the sodium tartrate aqueous solution of 0.5M is (as electrolytic solution, to allocate and make by sodium tartrate and water, pH value is 7.8) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain electrolyzer for the first time.By adjusting this power supply unit, make this for the first time the current density of electrolyzer be controlled at 40A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this stainless steel wire carries out electrolysis treatment for the first time.
Until electrolysis treatment after 60 seconds, take out this through the stainless steel wire of once electrolytic processing and using it as anode, put into concentration and be the trisodium phosphate aqueous solution of 0.5M (as electrolytic solution, to allocate and make by tertiary sodium phosphate and water, pH value is 13) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain electrolyzer for the second time.By adjusting this power supply unit, make this for the second time the current density of electrolyzer be controlled at 40A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this stainless steel wire carries out electrolysis treatment for the second time.
Until electrolysis treatment for the second time after 60 seconds, take out this through the stainless steel wire of electrolysis treatment for the second time and be positioned in a ultrasonic vibrating device and shake, lasting after 60 seconds, then (3M company manufactures with cloth, model is 8501) carry out brushing, make a cloudy surface stainless steel.
Outward appearance is observed
By the outward appearance of visual inspection embodiment 18 prepared stainless steels, result is as shown in table 5 below.
Comparative example 5 and 6
Comparative example 5 and 6 is to carry out electrolytic derusting according to the same steps flow process of embodiment 18, utilizes same steps to carry out outward appearance observation simultaneously, and difference is: comparative example 5 is using the sodium citrate aqueous solution of 0.5M as the electrolytic solution of electrolysis treatment for the first time; Comparative example 6 is using the aqueous sodium hydroxide solution of 0.5M as the electrolytic solution of electrolysis treatment for the first time.Test result arranges respectively in following table 5.
Table 5
Figure BDA0000407680160000111
Interpretation of result: as shown in Table 5, the scale removal effect of embodiment 18 is best, proves that electrolysis treatment is used the sodium tartrate aqueous solution to contribute to the removal of follow-up scale as electrolytic solution for the first time.
Embodiment 19
First get stainless steel wire that a surface has black scale (purchased from Hua Xin stainless steel company, model is SS316, the diameter of stainless steel wire is 5.5mm, length is 50mm, scale thickness be 20 μ m), it is elementary composition as shown in table 6 below, and EDS analyzes photo as shown in Figure 6, and each composition ratio distributes as shown in Figure 7.Again using this stainless steel wire as anode, and to put into concentration be that the sodium tartrate aqueous solution of 0.5M is (as electrolytic solution, to allocate and make by sodium tartrate and water, pH value is 7.8 to 8) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain electrolyzer for the first time.By adjusting this power supply unit, make this for the first time the current density of electrolyzer be controlled at 20A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this stainless steel wire carries out electrolysis treatment for the first time.
Table 6
Figure BDA0000407680160000112
Until electrolysis treatment after 60 seconds, take out this stainless steel wire through electrolysis treatment and utilize and be serially connected with energy dispersion x-ray spectrometer (energy dispersive X-ray spectroscopy, EDS) sweep electron microscope (SEM) is observed the scale be full of cracks degree after electrolysis treatment, and sample in the time amplifying 40 times, it is elementary composition as shown in table 7 below, EDS analyzes photo as shown in Figure 8, each composition ratio distributes as shown in Figure 9, the simultaneously composition of test surfaces scale, outward appearance photo as shown in figure 10 and test result as shown in table 8 below.
Table 7
Using the stainless steel wire testing as anode, put into concentration and be the trisodium phosphate aqueous solution of 0.5M (as electrolytic solution, to allocate and make by tertiary sodium phosphate and water, pH value is 13) in, then respectively this anode and negative electrode (being made up of pure titanium metal) are electrically connected to a power supply unit, to obtain electrolyzer for the second time.By adjusting this power supply unit, make this for the second time the current density of electrolyzer be controlled at 40A/dm 2, and the temperature of adjusting electrolytic solution is 31 ℃, so that this stainless steel wire carries out electrolysis treatment for the second time.
Until electrolysis treatment for the second time after 60 seconds, take out this through the stainless steel wire of electrolysis treatment for the second time and be positioned in a ultrasonic vibrating device and shake, lasting after 60 seconds, then (3M company manufactures with cloth, model is 8501) carry out brushing, make a cloudy surface stainless steel.
Outward appearance is observed
By the outward appearance of visual inspection embodiment 19 prepared stainless steels, result is as shown in table 8 below.
Embodiment 20 to 23
Embodiment 20 to 23 carries out electrolytic derusting according to the same steps flow process of embodiment 19, utilizes same steps to carry out outward appearance observation simultaneously, and difference is: the current density of the electrolysis treatment for the first time of embodiment 20 to 23 is different from embodiment 19.Outward appearance photo respectively as shown in Figure 11, Figure 12, Figure 13 and Figure 14 and test result arrange respectively in following table 8.
Comparative example 7
Get stainless steel wire that a surface has black scale (purchased from Hua Xin stainless steel company, model is SS316, the diameter of stainless steel wire is 5.5mm, length is 50mm, scale thickness be 20 μ m), recycling is serially connected with energy dispersion x-ray spectrometer (energy dispersive X-ray spectroscopy, EDS) sweep electron microscope (SEM) is observed the outward appearance without electrolysis treatment, and sample in the time amplifying 40 times, the simultaneously composition of test surfaces scale, outward appearance photo as shown in figure 15 and test result as shown in table 8 below.
Table 8
Interpretation of result: the result by Figure 10 to Figure 15 can be found, when current density is 60A/dm 2when above, there is obvious crack performance through the scale on the stainless steel wire surface of electrolysis treatment, be conducive to shorten the treatment time of follow-up ultrasonic vibrating and brushing.As shown in Table 8, when current density is 60A/dm 2when above, the content of oxygen is obviously reduced to 5.44 by 48.4, represents that the content of oxide compound reduces, and also proves that working as current density is 60A/dm simultaneously 2when above, rust cleaning efficiency is better.
Embodiment 24 to 27
Embodiment 24 to 27 carries out electrolytic derusting according to the same steps flow process of embodiment 18, utilize same steps to carry out outward appearance observation, difference is simultaneously: concentration of electrolyte and the current density of the electrolysis treatment for the first time of embodiment 24 to 27 are different from embodiment 18.Electrolysis treatment condition and test result arrange respectively in following table 9.
In addition, utilize following flow process assessment scale to remove degree: utilize hundred lattice scale computing methods to assess scale and remove degree, result is as shown in table 9 below.When scale degree is A, represent that rust cleaning rate is 95%; When scale degree is B, represent that rust cleaning rate is 90%; When scale degree is C, represent that rust cleaning rate is 85%; When scale degree is D, represent that rust cleaning rate is 80%.The acceptable rust cleaning rate of industry is more than 90% at present, and namely scale degree is required to be A or B.
Comparative example 8
Comparative example 8 is to carry out electrolytic derusting according to the same steps flow process of embodiment 18, and difference is: concentration and the current density of the sodium tartrate aqueous solution of the electrolysis treatment for the first time of comparative example 8 are different from embodiment 18.Electrolysis treatment condition and test result refer to following table 9.
Table 9
Figure BDA0000407680160000141
Interpretation of result: the result by table 9 can find, the scale of embodiment 24 to 27 is removed degree can meet industry demand, and the surface of prepared stainless steel is level and smooth cloudy surface really.The surface of comparative example 8 prepared stainless steels is structure unfairness cloudy surface.
Embodiment 28 and comparative example 9
Embodiment 28 and comparative example 9 are to carry out electrolytic derusting according to the same steps flow process of embodiment 26, utilize same steps to carry out outward appearance observation, difference is simultaneously: the electrolytic solution of the electrolysis treatment for the second time of embodiment 28 is by the trisodium phosphate aqueous solution of the 0.5M of 500mL is mixed obtained with the aqueous citric acid solution (20g citric acid is added in 500mL water and prepared) of the 0.5M of 500mL; The electrolytic solution of the electrolysis treatment for the second time of comparative example 9 is by the dissolution of sodium hydroxide of the sodium-chlor of 125g and 10g is obtained in the water of 500mL.Electrolysis treatment condition and test result arrange respectively in following table 10.
Table 10
Figure BDA0000407680160000151
Interpretation of result: embodiment 28 is in using the mixed solution of trisodium phosphate aqueous solution and aqueous citric acid solution as electrolytic solution in electrolysis treatment for the second time; scale can be departed from from stainless steel surface; and trisodium phosphate aqueous solution can soften stainless steel surface and form fine and close said minuscule hole; after brushing, will form one deck phosphoric acid epithelium, more can effectively protect the surface of stainless steel.Comparative example 9 is because of the easy corroding metal of the chlorion in sodium-chlor, then after electrolysis treatment, more accelerates erosion rate, makes stainless steel surface produce great hole.
Embodiment 29 to 41, comparative example 10 and 11
Embodiment 29 carries out electrolytic derusting according to the same steps flow process of embodiment 28, utilizes same steps to carry out outward appearance observation simultaneously.Embodiment 30 to 41, comparative example 10 and 11 are the same steps flow process electrolytic derustings according to embodiment 28, utilize same steps to carry out outward appearance observation, difference is simultaneously: the current density of the electrolysis treatment for the second time of embodiment 30 to 32 and comparative example 10 is different from embodiment 28; Concentration of electrolyte and the current density of the electrolysis treatment for the second time of embodiment 33 to 36 and comparative example 11 are different from embodiment 28; Temperature and the current density of the electrolysis treatment for the second time of embodiment 37 to 41 are different from embodiment 28.Electrolysis treatment condition and test result arrange respectively in following table 11 (it is to carry out according to the same steps of embodiment 24 to 27 that scale is removed Tachistoscope).
Table 11
Figure BDA0000407680160000161
The scale of interpretation of result: embodiment 29 to 41 is removed degree and is all met industry demand, proof for the first time electrolysis treatment is used the sodium tartrate aqueous solution, electrolysis treatment is used the mixed solution of trisodium phosphate aqueous solution and aqueous citric acid solution for the second time, really can effectively remove scale and make cloudy surface stainless steel.
Embodiment 29 to 32 is compared with comparative example 10, can find that the current density of electrolysis treatment is 40A/dm for the second time 2when above, can obtain preferably scale and remove degree.
Embodiment 33 to 36 is compared with comparative example 11, can find when the concentration of the electrolytic solution of electrolysis treatment be for the second time 0.3M when above, can obtain preferably scale removal degree.
The result of comparing embodiment 37 to 41, can find that the impact that the temperature of electrolysis treatment is removed degree for scale is for the second time little.Not excessive temperature during higher than 60 ℃, still can obtain preferably scale and remove degree.
In sum, alkaline electrolysis derusting method of the present invention utilizes neutrality or alkaline electrolysis mode, and by using the specific alkaline electrolyte that contains sodium tartrate, can allow the steel that make there is level and smooth and bright surface.Method of the present invention also, without through electrolysis treatment repeatedly, not only meets economic benefit, more meets the demand of environmental protection.
Only as described above, be only the preferred embodiments of the present invention, when not limiting scope of the invention process with this, i.e. every simple equivalence of doing according to claim scope of the present invention and description changes and modifies, and all belongs in the scope that the present invention contains.

Claims (16)

1. an alkaline electrolysis derusting method, it comprises following steps:
(A) steel that, provide a surface to contain scale;
(B), make steel that described surface contains scale as anode, then insert in an alkaline electrolyte that contains tartrate and carry out alkaline electrolysis processing, this concentration of electrolyte is more than or equal to 0.4M, and the current density of electrolysis is more than or equal to 10A/dm 2, to obtain the steel through electrolysis treatment; And
(C), provide a mechanical force to the described steel through electrolysis treatment, until scale depart from from the surface of these steel and make the steel of a surface without scale.
2. alkaline electrolysis derusting method as claimed in claim 1, wherein, the tartrate in step (B) is one or more the combination being selected from sodium tartrate, soluble tartrate and sodium-potassium tartrate.
3. alkaline electrolysis derusting method as claimed in claim 1, wherein, step (B) is to carry out under 7 to 8.5 pH value scope.
4. alkaline electrolysis derusting method as claimed in claim 1, wherein, the current density range of the electrolysis treatment in step (B) is 20 to 160A/dm 2.
5. alkaline electrolysis derusting method as claimed in claim 1, wherein, step (B) is to carry out under the temperature range of 30 to 70 ℃.
6. alkaline electrolysis derusting method as claimed in claim 1, wherein, the alkaline electrolyte that contains tartrate in step (B) is the sodium tartrate aqueous solution.
7. alkaline electrolysis derusting method as claimed in claim 6, wherein, the concentration range of the described sodium tartrate aqueous solution is 0.8 to 1.0M.
8. alkaline electrolysis derusting method as claimed in claim 1, wherein, the mechanical force in step (C) is provided by the mode of following formed group: the combination of one or more in brushing, wiping and ultrasonic vibrating.
9. alkaline electrolysis derusting method as claimed in claim 1, it more comprises one in step (B) step (B1) afterwards, this step (B1) is to make the described steel through electrolysis treatment as anode, insert again in an alkaline electrolyte that contains tertiary sodium phosphate and carry out electrolysis treatment for the second time, to obtain through the steel of electrolysis treatment for the second time.
10. alkaline electrolysis derusting method as claimed in claim 9, wherein, more contains a metal chelator in the alkaline electrolyte of described phosphoric acid trisodium.
11. alkaline electrolysis derusting methods as claimed in claim 10, wherein, described metal chelator is to be selected from citric acid, sodium-chlor or both combinations.
12. alkaline electrolysis derusting methods as claimed in claim 9, wherein, the current density range of the electrolysis treatment for the second time in step (B1) is 20 to 160A/dm 2.
13. alkaline electrolysis derusting methods as claimed in claim 9, wherein, step (B1) is to carry out under the temperature range of 30 to 70 ℃.
14. alkaline electrolysis derusting methods as claimed in claim 9, wherein, the alkaline electrolyte of the phosphoric acid trisodium in step (B1) is trisodium phosphate aqueous solution.
15. alkaline electrolysis derusting methods as claimed in claim 14, wherein, the concentration range of described trisodium phosphate aqueous solution is 0.2 to 0.6M.
16. alkaline electrolysis derusting methods as claimed in claim 1, wherein, more contain polyoxyethylene glycol in described alkaline electrolyte.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105965362A (en) * 2016-06-30 2016-09-28 国网安徽省电力公司全椒县供电公司 Rust removal process for switch cabinet
CN106048708A (en) * 2016-07-22 2016-10-26 昆明理工大学 Electrolytic polishing method for titanium alloy
CN106048708B (en) * 2016-07-22 2017-12-01 昆明理工大学 A kind of method of titanium alloy electrobrightening
CN106591933A (en) * 2017-01-20 2017-04-26 王玉田 Electrolyte capable of removing oil and rust of metal surfaces
CN107059106A (en) * 2017-04-18 2017-08-18 安徽华辉塑业科技股份有限公司 A kind of liquid pump blade derusting method
CN107419325A (en) * 2017-08-16 2017-12-01 太仓市顺昌锻造有限公司 A kind of derusting method of steel
CN109778293A (en) * 2019-02-28 2019-05-21 苏州纳孚林科金属表面技术有限公司 A kind of electrolytic derusting antirust agent
CN110923797A (en) * 2019-11-08 2020-03-27 东莞市国瓷新材料科技有限公司 Process for improving DPC electroplating hole filling uniformity by utilizing electrolytic cleaning and cleaning

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