CN107747096B - A kind of method of stainless steel surface roughening treatment - Google Patents
A kind of method of stainless steel surface roughening treatment Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- C23F1/28—Acidic compositions for etching iron group metals
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Abstract
The invention belongs to technical field of material surface treatment, more particularly to a kind of method of stainless steel surface roughening treatment, the following steps are included: 1) sand surface treatment: the stainless steel Jing Guo pre-treatment being immersed in sand surface treatment agent, forms micron order rough surface in stainless steel surface；2) surface clean: stainless steel obtained by step 1) is immersed in strong acid cleaning solution, the loose tractionless copper of clean the surface and stannous chloride adsorption layer appear the micron order rough surface of stainless steel surface；3) it shows sand processing: stainless steel obtained by step 2) is immersed in aobvious sand treatment fluid, form nanoscale rough face on stainless steel micron order rough surface；4) surface adjusts: stainless steel obtained by step 3) being immersed in surface adjustment liquid, appears stainless steel from micron order to nanoscale rough surface.The present invention can be roughened the rough surface to be formed and arrive 10-400nm with 1-40 μm, can effectively improve the adhesive force of stainless steel and surface attachments, increase its bond strength.
Description
Technical field
The invention belongs to technical field of material surface treatment, in particular to a kind of method of stainless steel surface roughening treatment.
Background technique
Stainless steel material is stablized, and is not easy to be oxidized and corrode, and has very strong hardness and rub resistance power, at present gradually
Favored by fields such as digital communication equipment, electronic apparatus manufactures, however stainless steel has difficult processing because of its special performance again
Etc. drawbacks, be greatly limited stainless steel in terms of roughing in surface.Roughened stainless steel can be applied to multiple fields,
If Material Field does with porous stainless steel filter the separation and storage of the isotope of hydrogen, health field uses porosity
Stainless steel injects antibacterial material to achieve the purpose that reduce germ contamination, and medical domain does drug load using porosity stainless steel
Body, and by the modified compatibility for enhancing itself and organism, the stainless steel nanometer Jing Guo roughening treatment is infused in digital communication field
Moulding increases Performance Strength and the superior appearance of generation of communication apparatus etc. at center.
Traditional stainless steel surface processing is exactly by mechanical grinding, sandblasting or to use strong acid such as nitric acid, hydrofluoric acid, chromium
The corrosivity medicament such as acid carries out chemistry or electrochemical treatments, with the improvement of people's environmental awareness, and at present to stainless steel watch
Face is roughened the raising for requiring degree, the method for emerging various stainless steel surface roughening treatments in the market, such as patent
CN101215703A, patent CN101215699A etc. are using inorganic acid and organic acid to stainless steel surface under conditions of heating
It carries out whitening sand surface treatment, realizes stainless steel watch by the way of patent CN104117833B is electrolysed using plasma, laser is polished
Face roughening, patent CN102234806B are realized under medium temperature using ferric trichloride, hydrochloric acid, nitric acid etc. to stainless steel watch facet etch
Roughening, patent CN105002499A, patent CN103163004A, patent CN101368889A etc. are used based on picric acid,
Copper chloride, iron chloride, hydrochloric acid, nitric acid etc. arrange in pairs or groups to corrode stainless steel surface to achieve the purpose that coarse surface, show crystal phase.This
Class corrosion roughening is mostly to be extremely difficult to produce stainless steel surface for the purpose of delustring, exposed lattice in addition to iron chloride etch systems
Raw more strong roughening, corrosivity is too strong again for iron chloride etch systems, if can carry out to stainless steel whole without masking
Body corrosion consumption, is equally difficult to reach the very big rough surface of roughness.
In view of this, it is necessory to provide a kind of technical solution to solve the above problems.
Summary of the invention
It is an object of the invention to: in view of the deficiencies of the prior art, and provide a kind of side of stainless steel surface roughening treatment
Method, the present invention take substep etch to produce multi-level rough surface in stainless steel surface, and roughness Ra is micro- from 1-40 μm
Meter level level progressively increases to the nanoscale of 10-400nm, and the rough surface of each level is substantially uniformly existing.
In order to realize above-mentioned purpose, the invention adopts the following technical scheme:
A kind of method of stainless steel surface roughening treatment, includes the following steps:
1) sand surface treatment: the stainless steel Jing Guo pre-treatment is immersed in the sand surface treatment agent based on acidic copper chloride
Carry out the roughening treatment of sand face, form micron order rough surface in stainless steel surface, wherein the sand surface treatment agent be with copper chloride,
Hydrochloric acid, small organic molecule carboxylic acid, Azole Corrosion Inhibitors, wetting agent compound.
Sand surface treatment step takes the copper chloride of 300-500g/L, the small organic molecule carboxylic acid of 20-200g/L, 1-10g/L
Azole Corrosion Inhibitors, the low-foam wetting agents of 1-10g/L corrode 1-5 minutes at 70-90 DEG C, repeat 1-3 times.The purpose is to utilize
The corrosivity and particularity of copper chloride and small organic molecule acid generate micron order rough surface in stainless steel surface and form one layer of richness
The conversion coating of cupric and copper compound.Stainless steel is because being rich in chromium, and surface is easy to form the hydroxide passivating film of chromium, to lead
Stainless steel is caused to be difficult to be processed corrosion, it, can be with according to electrode potential however after the hydroxide passivating film of this layer of chromium is destroyed
Find out, The stainless steel of activation can be easy to be chlorinated copper corrosion corrosion.
Secondly inherently there is some defects such as oxide to be mingled with a little on its surface when stainless steel generates processing, herein generally all
It is the anode region as corrosion cell, it is easy to the erosion for causing chloride ion and this kind of aggressive agent of small molecule acid ion, in chlorine
Under the infiltration of ion and small organic molecule acid, these positions just be will form such as cavitation corrosion shape a large amount of on Fig. 1,2, and institute of the present invention
The small organic molecule acid of selection is the small carboxylic acid molecules with very strong electron attraction, such as halogen formate, acetic acid or propionic acid, this
Class aggressive agent is indispensable ingredient in stainless steel surface roughening treatment, it is a kind of anode accelerator, this is to be based on
This kind of aggressive agent is easy to be attracted to the electrode surface with oxidation film, and the oxonium ion in oxidation film can be replaced to generate chlorine
Compound or carboxylic acid object and the dissolution for causing stainless steel.
Under certain temperature, acidity and copper chloride concentration, copper chloride is to close copper acid H with the stronger tetrachloro of corrosivity2
[CuCl4] form presence, when the stainless steel watch face contact with activation, it obtains the copper ion that electronics becomes monovalence, stainless steel
Interior nickel, iron and chromium loses electronics and becomes bivalent nickel ion, ferrous ion and trivalent chromic ion, and the copper ion of monovalence is a large amount of
Generate the stannous chloride dimer for being insoluble in water in the presence of chloride ion, the stannous chloride dimer of generation insoluble in solution and
Itself has certain viscosity, is adsorbed on stainless steel surface, on the micro level, so that copper chloride corrosive liquid be prevented to continue and adsorb
There is stannous chloride position stainless steel to generate corrosion, and stannous chloride corrosion itself generates, therefore this layer of adsorption layer itself
It is exactly porous discontinuous, therefore the reaction was continued for partial portion, under certain acidity and copper chloride concentration, stainless steel surface is just
Non-uniform corrosion can be continued to generate to generate non-uniform rough surface.According to movable metallic sequence list and actual experiment table
It is bright, during generating stannous chloride along with chlorination copper corrosion, it there is also the displacement of metallic copper, the metallic copper of generation is again
Stannous chloride can be generated by acidic copper chloride corrosion corrosion, and the copper that part has not enough time to reaction is then chlorinated cuprous sedimentary
It is wrapped up, one layer of conversion coating rich in copper and stannous chloride is collectively formed and is deposited on stainless steel surface.
2) surface clean: the stainless steel of step 1) sand surface treatment is immersed in strong acid cleaning solution, the loose nothing of clean the surface
The copper and stannous chloride adsorption layer of adhesive force appear the micron order rough surface of stainless steel surface, activate stainless steel surface, wherein institute
The strong acid cleaning solution stated is that hydrochloric acid, Thiourea corrosion inhibiter, wetting agent compound.
Surface cleaning step takes the hydrochloric acid of 300-500g/L, the Thiourea corrosion inhibiter of 1-10g/L, the wetting of 1-10g/L
Agent is cleaned 60-180 seconds in room temperature.The purpose is to remove the conversion coating of the loose no adhesive force copper of surface stainless steel and stannous chloride, chlorine
Change the cuprous ammonium hydroxide or hydrochloric acid for dissolving in high concentration, the ammonium hydroxide for being dissolved in high concentration forms complex compound, and the hydrochloric acid for being dissolved in high concentration is raw
At H3CuCl4Even and the stainless steel after being roughened still is easy to passivation, to increase activation effect, selects the hydrochloric acid of high concentration
Cleaning agent is made, the stannous chloride of surface porosity can be not only fallen with cleaning treatment, but also this layer of deposition of copper and stannous chloride will not be destroyed
Layer may also reach up the purpose that activation stainless steel promotes aobvious sand reaction.
3) it shows sand processing: stainless steel product obtained by step 2) being immersed in aobvious sand treatment fluid, aobvious sand treatment fluid is utilized
Selective corrosion forms nanoscale rough face on stainless steel micron order rough surface, wherein the aobvious sand treatment fluid is with sulphur
Acid, organic sulfonic acid, Thiourea corrosion inhibiter, wetting agent compound.
Aobvious sand processing step takes the sulfuric acid of 100-300g/L, the organic sulfonic acid of 100-300g/L, the Thiourea of 1-10g/L
Corrosion inhibiter, the wetting agent of 1-10g/L corrode 5-10 minutes at 60-80 DEG C, repeat 1-3 times.The purpose is to be existed using stainless steel
The principle corroded in sulfuric acid heating is corroded on the stainless steel with copper and stannous chloride sedimentary, because sulfuric acid does not corrode copper
And stannous chloride, to make stainless steel surface corrosion unevenly to achieve the purpose that nanoscale corrodes.Stainless steel has in sulfuric acid
There is activation-passive behavior, in the concentration of 100-300g/L, sulfuric acid shows as reproducibility, does not have oxidisability, easily generation hydrogen
Depolarising reaction.With SO in sulfuric acid solution4 2-、HSO4 -、H2O plasma occupies entire solution, under heating effect, corrosion reaction
The resistance to mass tranfer of aggravation, corrosion reaction reduces, secondly, the conductivity of sulfuric acid solution increases as temperature increases, anode and cathode reaction
Speed is accelerated；Stainless steel surface is deposited with the sedimentary of one layer of copper and stannous chloride, the electricity of copper after first step sand surface treatment
Electrode potential is higher than hydrogen, can inhibit sulfuric acid corrosion stainless steel evolving hydrogen reaction, and does not have the position of sedimentary, in sulfuric acid and organic sulphur
The action-reaction of acid generates soluble correspondence salt and partly precipitated and is attached to stainless steel surface.
Thiourea corrosion inhibiter is typically all to contain the heterocycles such as N, S, O and unsaturated bond, such as the most common thiocarbamide, to stainless steel
Inhibition be collective effect to anode and cathode, show as two kinds of forms of protonation type (Tu) and molecule-type in the solution,
Protonation type and H+In conjunction with formation TuH+, accelerate cathode hydrogen evolution reaction, molecule-type thiocarbamide is adsorbed on cathode and forms self-assembled film, resistance
Only corrosive medium and metal surface form contact surface；It can be generated uniform with balanced reaction by adding corrosion inhibiter in aobvious sand liquid
Suitable rough surface increases the roughness on surface.
4) surface adjusts: stainless steel obtained by step 3) being immersed in surface adjustment liquid, is cleaned remaining through sulfuric acid corrosion
The copper and stannous chloride sedimentary that grey black and sand surface treatment generate, appear stainless steel from micron order to nanoscale rough surface,
Wherein adjustment liquid in the surface is compounded with copper chloride, ammonium chloride, ammonium hydroxide, organic amine complexing agent.
Surface modification step takes the ammonia of the copper chloride of 50-100g/L, the ammonium chloride of 50-100g/L, 200-300ml/L
Water, 200-300ml/L organic amine impregnate at normal temperature 90-240 seconds.Similar PCB alkaline etching liquid system is taken in reaction, in body
The organic amine that Complexing Iron, nickel ion are introduced in system, its object is to first pass through similar PCB etching principle to wash away stainless steel surface
Copper and stannous chloride sedimentary, the loose no adhesive force that this layer of sedimentary has become in aobvious sand treatment fluid, and by drawing
The floating ash that the organic amine complexing stainless steel entered is generated in acid heating, cleans stainless steel surface, furthermore does resin subsequently selected
The organic amine adsorbed in rough surface when coating also gluing can occur at high temperature with resin and react, further increase resin with it is stainless
The adhesive force of steel surface.
Copper chloride and ammonium hydroxide complexing generate [Cu (NH3)4]Cl2, [Cu (NH3)4]Cl2[Cu (NH is generated with Cu again3)2] Cl, i.e.,
It is equal to the complex compound of stannous chloride and ammonium hydroxide, under the action of dissolved oxygen, and generates [Cu (NH3)4]Cl2, promote copper and chlorine
The dissolution for changing cuprous adsorption layer falls off.Stainless steel can always generate grey black in acid corrosion, and specific mechanism scientific circles there is no clear
Final conclusion is generally regarded as what the elements such as residue and nickel, iron, the chromium of the formation of the elements such as carbon, silicon a small amount of in stainless steel were formed
The complex compounds such as oxide, sulfide, usual stainless steel take acid with strong oxidizing property such as nitric acid, chromic acid etc. clear after surface treatment
Wash, both can thoroughly clean the surface grey black and have the function of be passivated stainless steel surface, however test show to take Strong oxdiative
Property acid cleaning stainless steel surface can destroy the nanoscale rough degree formed, be not achieved nanometer roughening stainless steel purpose,
After numerous studies, inventor is had surprisingly found that, the grey black through sulfuric acid corrosion can obtain in the alkaline amine system containing complexing agent
To remove and will not damage the nanoscale rough degree that stainless steel has been formed substantially, needed for can exposing through washing drying again at this time
Sand rough surface.
The present invention is to generate micron order rough surface and copper and chlorination in stainless steel surface using the corrosivity of sand surface treatment agent
Cuprous sedimentary, copper and stannous chloride sedimentary are adsorbed in micron order roughness face, and the profile arithmetic of the micron order rough surface is flat
Equal deviation Ra is between 1-40 μm, as shown in Figure 1, 2, corrodes stainless steel after surface clean, then through aobvious sand treatment fluid heating,
Continue to corrode on the basis of original micron order rough surface, because of copper and the inhibiting effect of stannous chloride sedimentary, so as to cause aobvious sand
The non-uniform corrosion for the treatment of fluid is further formed nanoscale rough degree in stainless steel surface, the profile arithmetic in the nanoscale rough face
Average deviation Ra is between 10-400nm, and as shown in Figure 5,6, the stainless steel surface by four step process has from micron order
To the rough surface of nanoscaled transition, the application performance on its surface is effectively improved.
As an improvement of the present invention, in the step 1), the pre-treatment includes conventional oil removing, derusting, work
Several pieces of stainless steel substrates are specifically such as soaked in degreaser 250~350 seconds, temperature is set as 55~65 DEG C by the processing such as change；Washing
It is soaked in again after clean in derusting activator 80-200 seconds, room temperature, then be soaked in weight percent 50% after washing completely
There is uniform bubble generation to stainless steel surface in hydrochloric acid solution, then washes clean be made.
As an improvement of the present invention, in the step 1), the small organic molecule carboxylic acid is that have strong electrophilic
The small carboxylic acid molecules of base, specifically can be formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, 2- chloropropionic acid,
2,2 dichloropropionic acid, 3- chloropropionic acid, 2,2,3- chloropon, a fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, 2,2- difluoro propionic acid,
At least one of 3,3,3- trifluoroacetic acid, five fluorine propionic acid；The Azole Corrosion Inhibitors are 2- tolimidazole, 2- sulfydryl benzene
And imidazoles, 2- methylbenzothiazole, 2-mercaptobenzothiazole, 2- methylbenzoxazole, 2- mercaptobenzoxazole, 2- methyl benzo
At least one of smile azoles, 2- sulfydryl benzo smile azoles；The wetting agent is polyethylene glycol, glycerine, fatty acid methyl ester ethoxy
At least one of based compound and sulfosuccinic acid methyl-isobutyl methyl esters salt.
As an improvement of the present invention, in the step 2), the Thiourea corrosion inhibiter be thiocarbamide, methylthiourea,
Dimethyl sulfourea, tetramethyl thiourea, ethyl thiourea, diethyl thiourea, n-propyl thiocarbamide, di-isopropyl thiourea, allylthiourea,
At least one of phenylthiourea, tolylthiourea, chlorphenyl thiocarbamide；The wetting agent is polyethylene glycol, glycerine, fat
At least one of sour methyl esters ethoxy compound and sulfosuccinic acid methyl-isobutyl methyl esters salt.
As an improvement of the present invention, in the step 3), the organic sulfonic acid is methane sulfonic acid, trifluoro methylsulphur
Acid, ethylsulfonic acid, isethionic acid, sulfamic acid, NSC 209983, benzene sulfonic acid, 4- hydroxy benzene sulfonic acid, 4- chlorobenzenesulfonic acid, 4-
At least one of toluenesulfonic acid, 3- aminobenzenesulfonic acid；The Thiourea corrosion inhibiter is thiocarbamide, methylthiourea, dimethyl
Thiocarbamide, tetramethyl thiourea, ethyl thiourea, diethyl thiourea, n-propyl thiocarbamide, di-isopropyl thiourea, allylthiourea, phenyl sulphur
At least one of urea, tolylthiourea, chlorphenyl thiocarbamide；The wetting agent is polyethylene glycol, glycerine, fatty acid methyl ester
At least one of ethoxy compound and sulfosuccinic acid methyl-isobutyl methyl esters salt.
As an improvement of the present invention, in the step 4), the organic amine is hydrazine hydrate, triethanolamine, diethyl
Hydramine, monoethanolamine, diethylenetriamine, triethylene tetramine, triisopropanolamine, ethylenediamine, at least one in tetramethylethylenediamine
Kind.
Beneficial effects of the present invention: the present invention by sand surface treatment step, surface cleaning step, aobvious sand processing step, with
And surface modification step enables stainless steel surface to generate from micron order to nanoscale rough surface, it is easy especially for hardly possible corrosion
The stainless steel of passivation has remarkable result, such as common 304,316L, 2205 series stainless steels can use side of the invention
Method forms the micron order with 1-40 μm to the nanoscale rough face of 10-400nm in roughing in surface, and generate through the invention
Rough surface can significantly improve the adhesive force of stainless steel Yu surface attachments (such as resin), substantially increase bond strength, have
Effect promotes the application performance of stainless steel.
Detailed description of the invention
Fig. 1 is to scan after the processing method of the embodiment of the present invention 1 is handled to c) surface cleaning step through SU-70 thermal field emission
The picture that Electronic Speculum is observed after amplifying 300 times.
Fig. 2 is to scan after the processing method of the embodiment of the present invention 1 is handled to c) surface cleaning step through SU-70 thermal field emission
The picture that Electronic Speculum is observed after amplifying 1k times.
Fig. 3 is to scan after the processing method of the embodiment of the present invention 1 is handled to c) surface cleaning step through SU-70 thermal field emission
The picture that Electronic Speculum is observed after amplifying 10k times.
Fig. 4 is to scan after the processing method of the embodiment of the present invention 1 is handled to c) surface cleaning step through SU-70 thermal field emission
The picture that Electronic Speculum is observed after amplifying 20k times.
Fig. 5 is to scan after the processing method of the embodiment of the present invention 1 is handled to e) surface modification step through SU-70 thermal field emission
The picture that Electronic Speculum is observed after amplifying 10k times.
Fig. 6 is to scan after the processing method of the embodiment of the present invention 1 is handled to e) surface modification step through SU-70 thermal field emission
The picture that Electronic Speculum is observed after amplifying 50k times.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, below in conjunction with specific embodiment and Figure of description,
Technical solution of the present invention is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of labour.
Embodiment 1
A kind of method of stainless steel surface roughening treatment, includes the following steps:
A) it pre-treatment: by the 316L stainless steel cut of commercially available 1.0mm thickness at the small pieces of many 15mm × 50mm, takes at random
Ten securely hang over it on titanium alloy hanger；Then it is soaked in stainless steel degreaser 300 seconds, temperature is set as 60 DEG C；Washing
It is soaked in again after clean in derusting activator 120 seconds, room temperature；The hydrochloric acid that volumetric concentration is 50% is soaked in after washing completely again
180 seconds in aqueous solution, room temperature；
B) sand surface treatment: the stainless steel substrates of a) step process being put into sand surface treatment slot and impregnate 5min, and washing is clean
After repeat and impregnate 5min, washing is clean, and temperature is set as 80 DEG C, wherein sand surface treatment slot: copper chloride 400g/L, trichloroacetic acid
80g/L, 2-mercaptobenzothiazole 5g/L, polyethylene glycol 5g/L；
C) surface clean: the stainless steel of b) step process is immersed in rinse bath and is impregnated 90 seconds, temperature is set as room temperature, water
Wash clean, wherein rinse bath: hydrochloric acid 300g/L, methylthiourea 3g/L, polyethylene glycol 5g/L；1 316L stainless steel is taken at random,
Using SU-70 thermal field emission scanning electron microscopic observation through the stainless steel surface that c) step surface clean obtains, as shown in Figure 1, 2, see
It is the 1-40 μm of rough surface covered that stainless steel surface, which is observed, with profile arithmetic average error Ra, continues to expand amplification factor, such as
Fig. 3, shown in 4, micron order roughness can't see, and stainless steel surface, which is also no longer able to observation, sand surface roughness；
D) it shows sand processing: the stainless steel of c) step process being immersed in aobvious sand processing and is impregnated 10 minutes, temperature is set as 70
DEG C, washing is clean, wherein aobvious sand treatment trough: sulfuric acid 200g/L, methane sulfonic acid 200g/L, methylthiourea 3g/L, polyethylene glycol are
5g/L；
E) surface adjusts: the stainless steel of d) step process is immersed in table tune slot and is impregnated 200 seconds, temperature is set as room temperature,
It is dried after washing is clean, wherein table tune slot: copper chloride 60g/L, ammonium chloride 60g/L, ammonium hydroxide 250ml/L, triethanolamine 250ml/
L takes 1 316L stainless steel at random, is adjusted using SU-70 thermal field emission scanning electron microscopic observation through e) step surface stainless
Steel surface, observing that surface has profile arithmetic average error Ra is the rough surface of 1-40 μm of covering, continues to expand amplification factor,
As shown in Figure 5,6, observing stainless steel surface to have profile arithmetic average error Ra is the rough surface of 10-400nm covering.
Embodiment 2
Using ten 316L stainless steel substrates of step process identical in embodiment 1, the difference is that: b) step is by trichlorine
Acetic acid changes trifluoroacetic acid into, and weight is constant, and polyethylene glycol changes glycerine into, and weight is constant；D) methane sulfonic acid changes into step
4- hydroxy benzene sulfonic acid, weight are constant；Taken at random from ten 316L stainless steels after c) step it is a piece of, using SU-70 thermal field send out
Scanning electron microscopic observation is penetrated through the stainless steel surface that c) step surface clean obtains, observes that stainless steel surface is flat with profile arithmetic
Equal deviation Ra is the rough surface of 1-40 μm of covering, continues to expand amplification factor, micron order roughness can't see at this time, no
Rust steel surface, which is also no longer able to observation, sand surface roughness；It takes a piece of, adopts at random from nine 316L stainless steels after e) step
With SU-70 thermal field emission scanning electron microscopic observation through the stainless steel surface that e) step surface adjusts, observe that surface has wheel
Wide arithmetic average deviation Ra is the rough surface of 1-40 μm of covering, continues to expand amplification factor, observes that stainless steel surface has wheel
Wide arithmetic average deviation Ra is the rough surface of 10-400nm covering.
Embodiment 3
Using ten stainless steel substrates of step process identical in embodiment 1, the difference is that: a) step is by ten 316L
Stainless steel substrates change 304 stainless steel substrates into；B) copper chloride adjusts 350g/L, c in step) sulfuric acid is adjusted to 150g/L, first in step
Base sulfonic acid is adjusted to 150g/L, remaining is constant；Taken at random from ten 304 stainless steels after c) step it is a piece of, using SU-70 heat
Field emission microscopy observation observes that stainless steel surface is calculated with profile through the stainless steel surface that c) step surface clean obtains
Art average deviation Ra is the rough surface of 1-40 μm of covering, continues to expand amplification factor, micron order roughness has not been seen at this time
Come, stainless steel surface, which is also no longer able to observation, sand surface roughness；One is taken at random from nine 304 stainless steels after e) step
Piece observes that surface has using SU-70 thermal field emission scanning electron microscopic observation through the stainless steel surface that e) step surface adjusts
Having profile arithmetic average error Ra is the rough surface of 1-40 μm of covering, continues to expand amplification factor, observes stainless steel watch mask
Having profile arithmetic average error Ra is the rough surface of 10-400nm covering.
Embodiment 4
Using ten 304 stainless steel substrates of step process identical in embodiment 3, the difference is that: b) step is by trichlorine
Acetic acid changes formic acid into, and weight is constant；C) methylthiourea changes di-isopropyl thiourea into step, and weight is constant；D) methyl in step
Sulfonic acid has changed sulfamic acid into, and weight is constant；E) triethanolamine changes hydrazine hydrate into step, and weight is constant；After c) step from
It takes a piece of in ten 304 stainless steels, is obtained using SU-70 thermal field emission scanning electron microscopic observation through c) step surface clean at random
Stainless steel surface, observing that stainless steel surface has profile arithmetic average error Ra is the rough surface of 1-40 μm of covering, continues to expand
Big amplification factor, micron order roughness can't see at this time, and stainless steel surface, which is also no longer able to observation, sand surface roughness；
Taken at random from nine 304 stainless steels after e) step it is a piece of, using SU-70 thermal field emission scanning electron microscopic observation through e) step table
The stainless steel surface that face adjusts, observing that surface has profile arithmetic average error Ra is the rough surface of 1-40 μm of covering,
Continue to expand amplification factor, observing that stainless steel surface has profile arithmetic average error Ra is the coarse of 10-400nm covering
Face.
Comparative example 1
Using 30 316L stainless steels of step process in embodiment 1, before 1. first taking ten 316L stainless steel substrates to be only a)
Drying is washed after processing step；2. washing drying after taking ten 316L stainless steel substrates only to do c) surface cleaning step again；3. last
The step of drying, i.e. complete embodiment 1 is washed after taking ten 316L stainless steel substrates to do e) surface cleaning step.Respectively to 30
Piece 316L stainless steel substrates make polyphenylene sulfoether resin mixture be bonded to 316L stainless steel surface by the way of injection molding, use
Tensile load method, which is measured, is measured 30 by the standard test method (ASTM D2919-2000) of the gluing bond strength of shearing force
The shearing force of 316L stainless steel and resin-bonded object measures the scheme 1. ten 316L stainless steels and polyphenylene Jing Guo pre-treatment
Sulfide resin is not bound with power, has voluntarily fallen off when repairing flash burr in test, bond strength 0, absolutely not residue glue；
Measurement scheme 2. the ten 316L stainless steels and polyphenylene sulfoether resin Jing Guo surface cleaning step bond strength about
36MPa has the residue glue of about half or so；3. measurement scheme passes through surface modification step (i.e. complete embodiment for ten
1) the bond strength about 39MPa of 316L stainless steel and polyphenylene sulfoether resin, substantially all full glue.
Comparative example 2
Using 30 304 stainless steels of step process in embodiment 3: place before 1. first taking ten 304 stainless steel substrates to be only a)
Drying is washed after managing step；2. washing drying after taking ten 304 stainless steel substrates only to do c) surface cleaning step again；3. finally taking ten
304 stainless steel substrates of piece do the step of drying, i.e. complete embodiment 1 is washed after e) surface cleaning step.Respectively to 30 304
Stainless steel substrates make polyphenylene sulfoether resin mixture be bonded to 304 stainless steel surfaces by the way of injection molding, negative using pulling force
Lotus method, which is measured, is measured 30 304 not by the standard test method (ASTM D2919-2000) of the gluing bond strength of shearing force
The shearing force of rust steel and resin-bonded object measures scheme 1. ten 304 stainless steels Jing Guo pre-treatment and polyphenylene sulfide tree
Rouge is not bound with power, has voluntarily fallen off when repairing flash burr in test, bond strength 0, absolutely not residue glue；Measurement side
The bond strength about 39MPa of case 2. ten 304 stainless steels and polyphenylene sulfoether resin Jing Guo surface cleaning step, has about
The residue glue of half or so；Measurement scheme 3. ten 304 stainless steels Jing Guo surface modification step (i.e. complete embodiment 1)
With the bond strength about 42MPa of polyphenylene sulfoether resin, substantially all full glue.
It can be seen that the stainless steel handled using processing method of the present invention, surface with comparative example from above-described embodiment
Roughness Ra value has the nanoscale transition from 1-40 μm of micron order to 10-400nm, not only has excellent sand face effect
Fruit can also significantly improve the bond strength between stainless steel and surface attachments (such as resin).
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (7)
1. a kind of method of stainless steel surface roughening treatment, which comprises the steps of:
1) sand surface treatment: the stainless steel Jing Guo pre-treatment is immersed in sand surface treatment agent, forms micron order in stainless steel surface
Rough surface, wherein the sand surface treatment agent is multiple with copper chloride, hydrochloric acid, small organic molecule carboxylic acid, Azole Corrosion Inhibitors, wetting agent
With forming；
2) surface clean: stainless steel obtained by step 1) is immersed in strong acid cleaning solution, the loose tractionless copper of clean the surface
And stannous chloride adsorption layer, stainless steel surface is activated, and appear the micron order rough surface of stainless steel surface, wherein the strong acid
Cleaning solution is compounded with hydrochloric acid, Thiourea corrosion inhibiter, wetting agent；
3) it shows sand processing: stainless steel obtained by step 2) is immersed in aobvious sand treatment fluid, it is rotten using the selectivity of aobvious sand treatment fluid
Erosion forms nanoscale rough face on stainless steel micron order rough surface, wherein the aobvious sand treatment fluid is with sulfuric acid, You Jihuang
Acid, Thiourea corrosion inhibiter, wetting agent compound, and the profile arithmetic average error Ra in the nanoscale rough face is in 10-
Between 400nm；
4) surface adjusts: stainless steel obtained by step 3) is immersed in surface adjustment liquid, is cleaned through the remaining grey black of sulfuric acid corrosion,
And the copper and stannous chloride sedimentary of sand surface treatment generation, appear stainless steel from micron order to nanoscale rough surface, wherein
The surface adjustment liquid is compounded with copper chloride, ammonium chloride, ammonium hydroxide, organic amine complexing agent.
2. the method for stainless steel surface roughening treatment according to claim 1, which is characterized in that at step 1) sand face
Pre-treatment in reason is to be soaked in stainless steel substrate in stainless steel degreaser 250~350 seconds, temperature is set as 55~65 DEG C；Water
It is soaked in again after wash clean in derusting activator 80~200 seconds；The salt that volumetric concentration is 50% is soaked in after washing completely again
150~200 seconds in aqueous acid.
3. the method for stainless steel surface roughening treatment according to claim 1, which is characterized in that at step 1) sand face
The agent of sand surface treatment is the copper chloride with 300-500g/L, the small organic molecule carboxylic acid of 20-200g/L, the azole of 1-10g/L in reason
The wetting agent of corrosion inhibiter, 1-10g/L compounds；The small organic molecule carboxylic acid be formic acid, acetic acid, propionic acid, chloroacetic acid,
Dichloroacetic acid, trichloroacetic acid, 2- chloropropionic acid, 2,2 dichloropropionic acid, 3- chloropropionic acid, 2,2,3- chloropon, a fluoroacetic acid, difluoro
At least one of acetic acid, trifluoroacetic acid, 2,2- difluoro propionic acid, 3,3,3- trifluoroacetic acid, five fluorine propionic acid；The azole inhibition
Agent is 2- tolimidazole, 2-mercaptobenzimidazole, 2- methylbenzothiazole, 2-mercaptobenzothiazole, 2- methyl benzo evil
At least one of azoles, 2- mercaptobenzoxazole, 2- methyl benzo smile azoles, 2- sulfydryl benzo smile azoles；The wetting agent is poly-
At least one of ethylene glycol, glycerine, fatty acid methyl ester ethoxy compound and sulfosuccinic acid methyl-isobutyl methyl esters salt.
4. the method for stainless steel surface roughening treatment according to claim 1, which is characterized in that at step 1) sand face
The profile arithmetic average error Ra of the micron order rough surface formed is managed between 1-40 μm.
5. the method for stainless steel surface roughening treatment according to claim 1, which is characterized in that the step 2) surface is clear
Washing middle strong acid cleaning solution is the hydrochloric acid with 300-500g/L, the Thiourea corrosion inhibiter of 1-10g/L, the wetting agent compounding of 1-10g/L
It forms；The Thiourea corrosion inhibiter is thiocarbamide, methylthiourea, dimethyl sulfourea, tetramethyl thiourea, ethyl thiourea, diethyl
Thiocarbamide, n-propyl thiocarbamide, di-isopropyl thiourea, allylthiourea, phenylthiourea, tolylthiourea, in chlorphenyl thiocarbamide extremely
Few one kind；The wetting agent is that polyethylene glycol, glycerine, fatty acid methyl ester ethoxy compound and sulfosuccinic acid methyl are different
At least one of butyl methyl esters salt.
6. the method for stainless steel surface roughening treatment according to claim 1, which is characterized in that the step 3) is shown at sand
It is the sulfuric acid with 100-300g/L, the organic sulfonic acid of 100-300g/L, the Thiourea inhibition of 1-10g/L that sand treatment fluid is shown in reason
The wetting agent of agent, 1-10g/L compounds；The organic sulfonic acid is methane sulfonic acid, trifluoromethanesulfonic acid, ethylsulfonic acid, hydroxyl second
Base sulfonic acid, sulfamic acid, NSC 209983, benzene sulfonic acid, 4- hydroxy benzene sulfonic acid, 4- chlorobenzenesulfonic acid, 4- toluenesulfonic acid, 3- amino
At least one of benzene sulfonic acid；The Thiourea corrosion inhibiter is thiocarbamide, methylthiourea, dimethyl sulfourea, tetramethyl thiourea, second
Base thiocarbamide, diethyl thiourea, n-propyl thiocarbamide, di-isopropyl thiourea, allylthiourea, phenylthiourea, tolylthiourea, chlorobenzene
At least one of base thiocarbamide；The wetting agent is polyethylene glycol, glycerine, fatty acid methyl ester ethoxy compound and sulfo group
At least one of succinic acid methyl-isobutyl methyl esters salt.
7. the method for stainless steel surface roughening treatment according to claim 1, which is characterized in that step 4) surface tune
Whole middle surface adjustment liquid is the copper chloride with 50-100g/L, the ammonium chloride of 50-100g/L, the ammonium hydroxide of 200-300ml/L, 200-
The organic amine of 300ml/L compounds；The organic amine is hydrazine hydrate, triethanolamine, diethanol amine, monoethanolamine, diethyl
At least one of alkene triamine, triethylene tetramine, triisopropanolamine, ethylenediamine, tetramethylethylenediamine.
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| CN113652734B (en) * | 2021-08-23 | 2022-06-03 | 安徽工业大学 | Stainless steel surface electrolytic coarsening agent and coarsening method thereof |
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