CN102127784A - Electroplated Cu laminated film and preparation method thereof - Google Patents
Electroplated Cu laminated film and preparation method thereof Download PDFInfo
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Abstract
本发明涉及叠层膜的制备技术，具体为一种不仅具有优良耐磨、耐腐蚀性能，而且与基体材料结合强度高、可抑制裂纹的产生与扩展的电镀Cu叠层膜及其制备方法，解决为提高Cu镀层与基体材料的结合力而采用氰化物镀铜时产生的剧毒污染问题。本发明采用电镀工艺并间歇导入超声波的技术，制备了一种铜叠层镀膜，其制备方法：经过除油、净化处理的金属基底材料，进行电镀Cu叠层镀膜，当铜叠层镀膜达到所需要的厚度时，取出清洗干净并进行干燥后，即可得到制好的电镀Cu叠层镀膜。获得的金属铜膜呈层状结构，铜膜的单层厚度在0.08～2.5微米范围内，总厚度在3.2微米～50微米范围内根据实际需求可以进行调整。本发明简单易行、成本较低。The invention relates to the preparation technology of laminated films, specifically an electroplated Cu laminated film which not only has excellent wear resistance and corrosion resistance, but also has high bonding strength with base materials and can inhibit the generation and expansion of cracks and its preparation method. It solves the problem of highly toxic pollution produced when copper plating with cyanide is used to improve the bonding force between the Cu plating layer and the base material. The present invention adopts the technique of electroplating process and intermittently introducing ultrasonic waves to prepare a copper laminated film. The preparation method is as follows: the metal base material after degreasing and purification treatment is electroplated with Cu laminated film, and when the copper laminated film reaches the required When the required thickness is required, take it out, clean it and dry it, and then the prepared electroplated Cu laminated film can be obtained. The obtained metallic copper film has a layered structure, the single-layer thickness of the copper film is in the range of 0.08-2.5 microns, and the total thickness can be adjusted in the range of 3.2-50 microns according to actual needs. The invention is simple and easy to implement and has low cost.
Description
Technical field:
The present invention relates to the technology of preparing of stack membrane, be specially a kind of good wear-resisting, corrosion resistance nature that not only has, and with plating Cu stack membrane of body material bonding strength height, the generation that can suppress crackle and expansion and preparation method thereof.
Background technology:
The history in existing 170 years of electroplating technology development, and copper coating can obtain multicolour with the electrochemical coloring processing.Therefore, be widely used in the decoration of some archaizeding handicrafts, light fixture, toy, button and other small item.In order to guarantee to have good bonding force between copper coating and the metallic matrix, generally must approach copper (about 3 μ m) by elder generation's preplating one deck in cyanide copper plating solution, in hydrosulphate or pyrophosphate plating solution, thicken then.Contain highly toxic substance in the cyanide copper plating solution, not only human body is directly brought harm, and cause environmental pollution easily, also make the coating process more complicated that becomes in addition.
In recent years, have particular performances and obtained application gradually owing to ultrasonic technique in every field.Ultrasonic wave strengthens electroplating technology, is do not changing electroplate liquid formulation, do not increasing under the prerequisite of plating bath protection difficulty, changing a kind of novel method of coating performance and raising electroplating velocity significantly.Ultrasonic wave electroplate by sound jet strengthened the diffusion mass transfer process of plating bath, reduce concentration polarization, increase substantially the electrodeposition rate of the system that is subjected to the mass transfer diffusion control; The strengthening effect on its cavitation and microjet counter electrode surface can reduce the deposition overpotential, enlarges to allow current density range.To the difficult metal refining of part, can improve its deposition process conditions.The energy benefit that its cavatition produced has reduced electrode surface reduction of metal ion potential energy, has reduced critical nucleus radius, makes nucleation rate improve refinement coating crystal grain; In addition, under cavitation and the effect of high strength microjet, deposited to the broken of cathode surface, formed littler nucleus, caused " forming core propagation ", even crystal grain is stripped from cathode surface and is dissolved in the electrolytic solution again than coarse grain.When nucleation rate surpassed grain growth speed, crystal grain had just obtained refinement; Ultrasonic microjet and cavitation effect can in time be driven away the hydrogen of electrode surface absorption, thereby have reduced the hydrogen embrittlement that coating produces because of liberation of hydrogen, phenomenon such as grow dim, and reduce the coating internal stress.The counter electrode surface is constantly cleaned simultaneously, has reduced the deposition of impurity such as oxyhydroxide etc., can get rid of phenomenons such as coating is mingled with effectively.Ultrasonicly constantly clean electrode surface, make electrode surface obtain the successive activation, thereby the carrying out of promote the oxidation-reduction reaction prevents negative electrode and anode passivation towards jet.In composite electrodeposition, its cleanup action has improved the wetting conditions between particle and the solution, has promoted the deposition of particle.In the nano-composite plate preparation, can reduce the reunion of nano particle effectively, nano particle can be disperseed in plating bath effectively, and form even, smooth composite deposite with the metal ion codeposition.
Chinese invention patent (publication number CN1974870A) discloses a kind of method of ultrasonic wave reduction internal stress of electroplated copper film of material technology, the plating tank that fills electroplating solution is positioned in the ultrasonic bath, utilizes ultrasonication can effectively reduce the internal stress of electroplated copper film.Yet its weak point is: ultrasonic mechanism is crystal grain thinning, so just increases substantially the hardness of copper coating, and when dura mater was blocked up, the fragility tendency increased, and is easy to generate tiny crack and crack propagation.
Chinese invention patent (publication number CN1557997A) discloses the ultrasonic of a kind of nano level metal pottery---electro-deposition method, and the nano-particle material that the present invention uses is TiN, TiC, SiN, SiC and Al
2O
3One or more compositions, the nano functional film layer structure of its formation is tight, strength high toughness is good, and is firm with matrix bond, Rockwell hardness can reach more than the HRC60.Yet its weak point is: (1) TiN, TiC, SiN, SiC and Al
2O
3The nanostructure functional membrane coating that constitutes Deng film belongs to dura mater with dura mater is complementary, and the fragility tendency greatly.(2) its TiN, TiC, SiN, SiC and Al
2O
3All belong to the homogeneous dura mater Deng film, be easy to generate tiny crack and crack propagation.
Summary of the invention:
The object of the present invention is to provide a kind of good wear-resisting, corrosion resistance nature that not only has, and with high plating Cu stack membrane of body material bonding strength and preparation method thereof, solve the severe toxicity that produces when adopting cyanide copper plating and pollute, simplify problems such as the generation of crackle in coating process and the inhibition plated film and expansion for the bonding force that improves Cu coating and body material.
Technical scheme of the present invention is:
A kind of plating Cu stack membrane of high bond strength, this stack membrane is by intermittently introducing ultrasonic signal deposits the Cu plated film on metal base material in the electroplating technology process, the metal copper film that obtains is laminate structure, the thickness in monolayer of copper film is in 0.08～2.5 micrometer range, and total thickness can be adjusted in 3.2 microns～50 micrometer ranges according to the actual requirements.
The preparation method of the plating Cu stack membrane that described and matrix metal material bonding strength is high is substrate with the metallic substance, by intermittently introducing ultrasonic signal deposition Cu plated film, forms the Cu stack membrane in the electroplating technology process, and concrete steps are as follows:
(1) greasy dirt on the removal base metal surface cleans in organic solvent for ultrasonic;
(2) acid etching;
(3) washing;
(4) introduce ultrasonic signal, metal refining copper film on base material in the electroplating process discontinuous;
(5) wash and dry up, obtain the stack membrane of Cu.
In the described step (1), the greasy dirt of removing on the base metal surface is workpiece to be immersed in the trieline organic solution scrub;
In the described step (1), cleaning in organic solvent for ultrasonic is workpiece to be put into trieline organic solution cleaned 5～10 minutes by Ultrasonic Cleaners, makes workpiece obtain clean surface.
In the described step (2), acid etching is meant for different body materials selects suitable acid solution the oxide film on the matrix surface to be disposed the visible various plating handbooks of concrete grammar;
In the described step (4), introduce ultrasonic signal in the electroplating process discontinuous and be meant:
At first, be that 100～200mA, ultrasonic frequency are plated film 120～510 seconds under 16.5～55.5kHz at hyperacoustic electric current; Then, with the electric current of ultrasonic generator in 30 seconds by 100～200mA gradually (evenly) be reduced to 0; Then, do not adding under hyperacoustic state plated film 120～510 seconds; Again with the electric current of ultrasonic generator in 30 seconds by 0 gradually (evenly) be elevated to 100～200mA.Constantly repeat aforesaid operations, depositing time is 100～240 minutes, obtains the plating Cu stack membrane that needs.
In the described step (4), the current density of metal refining copper film process is 1～5A/dm on base material
2
Advantage of the present invention and beneficial effect are:
1, the present invention utilizes metal Cu element good electrical conductivity, thermal conductivity and abundant tinctorial property, with the metallic substance is substrate, in the electroplating technology process, deposit the Cu plated film by intermittently introducing ultrasonic signal, thereby obtain not only to have good wear-resisting, corrosion resistance nature, and with the Cu stack membrane of body material bonding strength height, the generation that can suppress crackle and expansion.
2, the present invention electroplates that Cu stack membrane preparation method is simple, cost is lower.
3, adopt the plating Cu stack membrane of the present invention's preparation, characteristics with laminate structure, the thickness in monolayer of copper film is in 0.08～2.5 micrometer range, total thickness can be adjusted in 3.2 microns～50 micrometer ranges according to the actual requirements, and the advantage of this structure mainly contains: the bonding strength height between (1) plated film and body material, plated film and the plated film; (2) wear-resisting, the corrosion resistance and good of plated film; (3) generation and the expansion of crackle be can suppress effectively, conventional ultrasonic electroplating film cracking and peeling phenomenon easily significantly improved.
Description of drawings:
Fig. 1 the present invention electroplates the end face electromicroscopic photograph of Cu stack membrane.
Fig. 2 the present invention electroplates the comparison of Cu stack membrane and the conventional Cu of plating film corrosion resistance nature.
Fig. 3 the present invention electroplates the comparison of Cu stack membrane and the conventional Cu of plating film wear resisting property.
Fig. 4 plated film bonding force is estimated isolated plant.
Among the figure, 1 clamp body; 2 bolts; 3 backing plates; 4 samples (sample).
Embodiment:
Embodiment 1
Through the surface removal greasy dirt, acid etching and washing are carried out in ultrasonic cleaning after 5 minutes in trieline organic solution, the 304 stainless steel base materials that clean up are connected on the negative electrode of electroplating power supply, anode adopts fine copper plate (copper content 99.7wt%), start ultrasonic generator, adjust its frequency and arrive 24.5kHz, electric current to 100mA, then plating piece is suspended to and begins in the electroplating solution that is placed in the ultrasonic cleaning tank to electroplate, the electroplating solution prescription is basic identical with the copper plating solution shown in the table 1 with processing parameter, and the current density that is added on the workpiece is 2A/dm
2During plated film to 150 second with the electric current of ultrasonic generator in 30 seconds gradually (evenly) be reduced to 0, do not adding under the ultransonic state plated film 150 seconds then, subsequently in 30 seconds again with the electric current of ultrasonic generator gradually (evenly) be elevated to 100mA, repeat this technological process, depositing time 240 minutes, thus deposition obtains the lamination plated copper film.This plated film is laminate structure, about 0.3 micron of present embodiment lamination Cu plated film thickness in monolayer, about 24 microns of plated film total thickness.As shown in Figure 1, from lamination Cu plated film section microscopic appearance as can be seen, plated film is tangible laminate structure, and about 0.3 micron of every layer thickness has good binding between plated film and the plated film.
Table 1 is electroplated Cu solution formula and processing parameter
| Component | Content (g/L) | Processing parameter | Technical indicator |
| CuSO 4·5H 2O | 200～250 | Current density | 1～5A/dm 2 |
| H 2SO 4 | 50～70 | Temperature/℃ | 25-30 |
| Glucose | 30～40 | Ultrasonic power | 220V 100～200mA |
| Water | Surplus | Ultrasonic frequency | 24.5KHz |
The present invention has carried out hardness test to common plating Cu film and the plating Cu stack membrane sample for preparing, and concrete testing method is as follows:
Testing apparatus: Japan makes SHIMAZU M84207 type microhardness tester; Load: 50gf;
Loading time: 15 seconds; Concrete operation method is as follows: at first with acetone specimen surface is cleaned up, then sample is placed on the sheet glass and (measures) towards last, determine between sample and the sheet glass behind the no gap, be put into together on the Stage microscope, observe specimen surface with 400 power microscopes earlier, determine to measure the hardness position, automatically loading 50gf then kept 15 seconds, demarcate the impression catercorner length, print hardness value, each sample is surveyed at 3 and is averaged.The hardness test result of Cu lamination plated film is 129.8Hv, and the hardness test result of common plating Cu film is 139.1Hv.
The present invention has carried out the polishing machine simultaneous test to common plating Cu film and the plating Cu stack membrane sample for preparing, and concrete experimental technique is as follows:
Experimental installation: Japan makes NUS-LSO-1 type emery wheel formula wear testing machine; Emery wheel sand paper: No. 1000 silicon carbide papers; Load: 6.4N; Electronic balance measuring accuracy: 0.1mg.Concrete operations are as follows:
At first with acetone specimen surface is cleaned up, blowing hot wind dries up specimen surface, measures and record sample initial weight.Then, sample is installed begins to carry out wearing test on the worktable, and each 100 change and guarantee that the sample surface of friction contact with fresh coated abrasive surface all the time.After each wearing test, utilize hairbrush that the friction surface cleaning is cleaned up specimen surface, dry up with acetone again after clean, measure also record sample weight, the weight loss of the changes in weight before and after the sample wearing test as sample.Successively, each sample may wear to and exposes till the matrix, and per 100 go round and round a millstone the average weight losses after decreasing of materialsing are passed judgment on the quality of plated film wear resisting property, and its weight loss bright plated film wear resisting property of saving your breath more is good more.Wearing test the results are shown in Fig. 2, and the wear resisting property of ultrasonic electroplating Cu stack membrane increases than common electrical deposited copper film as seen from the figure.
The present invention has carried out the corrosion resistance nature simultaneous test to common plating Cu film and the plating Cu stack membrane sample for preparing, and concrete experimental technique is as follows:
Adopt three-electrode cell and EG﹠amp; G 273A potentiostat is measured polarization curve, and testing liquid is the NaCl solution of 3.5wt%.Preceding test sample the envelope with Resins, epoxy of test is coated with, and making exposed area is 1cm
2Working electrode, supporting electrode is the Pt sheet, reference electrode is KCl, sweep velocity is selected 1mv/s.Fig. 3 is a test result, the corrosion potential of ultrasonic as can be seen acid copper film is obviously than the height of common electrical deposited copper film, from corrosion current only be the latter less than 1/2, corrosion resisting property of this explanation ultrasonic electroplating Cu stack membrane is greatly improved than common electrical deposited copper film.
The present invention has carried out the bonding force simultaneous test to common plating Cu film and the plating Cu stack membrane sample for preparing, and concrete experimental technique is as follows:
As shown in Figure 4, bending plated film bonding force evaluating apparatus about experimental installation adopts, mainly comprise clamp body 1, bolt 2 and backing plate 3, place two backing plates 3 between two clamp bodies 1 that are oppositely arranged, connect by bolt 2 between two clamp bodies 1, two backing plates 3, leave the gap that is used for plug-in mounting sample 4 between two backing plates 3, backing plate 3 tops are arc surface, and described arc surface diameter is 15 millimeters; The matrix of plated film sample 4 is 304 thick Stainless Steel Bands of 0.1mm, and concrete operations are as follows:
At first, with acetone that sample 4 surface cleaning are clean, blowing hot wind dries up specimen surface.Then, sample 4 is put between the arc surface of two backing plates 3 and by bolt 2 clamped.Earlier sample is spent and tension along left side arc surface crooked 180, again along crooked 180 degree of the right arc surface and tension, this operation that circulates, about each bending once as number of bends, till observing that plated film and base material are local and separating (bubbling appears in coated surface).Measurement result is listed in table 2, and the data of listing by table 2 are electroplated bonding strength between Cu stack membrane and the matrix and compared with the bonding strength between energising plating Cu film and the matrix and exceeded several times as can be seen.
Table 2 bonding force comparative test result
Embodiment 2
Difference from Example 1 is:
Through the surface removal greasy dirt, acid etching and washing are carried out in ultrasonic cleaning after 8 minutes in trieline organic solution, No. 45 steel as matrix material that clean up are connected on the negative electrode of electroplating power supply, anode adopts fine copper plate (copper content 99.7wt%), start ultrasonic generator, adjust its frequency and arrive 16.5kHz, electric current to 150mA, then plating piece is suspended to and begins in the electroplating solution that is placed in the ultrasonic cleaning tank to electroplate, the electroplating solution prescription is basic identical with the copper plating solution shown in the table 1 with processing parameter, and the current density that is added on the workpiece is 1A/dm
2During plated film to 120 second with the electric current of ultrasonic generator in 30 seconds gradually (evenly) be reduced to 0, do not adding under the ultransonic state plated film 120 seconds then, subsequently in 30 seconds again with the electric current of ultrasonic generator gradually (evenly) be elevated to 150mA, repeat this technological process, depositing time 100 minutes, thus deposition obtains the lamination plated copper film.This plated film is laminate structure, about 0.08 micron of present embodiment lamination Cu plated film thickness in monolayer, about 3.2 microns of plated film total thickness.
Present embodiment carries out wear resistance, corrosion resistance nature test to the plating Cu stack membrane for preparing, and has estimated the bonding strength between plated film and the matrix.Test-results shows, electroplates the Cu stack membrane and not only has good wear-resisting, corrosion resistance nature, and present superior film substrate bond strength.
Difference from Example 1 is:
Through the surface removal greasy dirt, acid etching and washing are carried out in ultrasonic cleaning after 10 minutes in trieline organic solution, the alloy matrix aluminum material that cleans up is connected on the negative electrode of electroplating power supply, anode adopts fine copper plate (copper content 99.7wt%), start ultrasonic generator, adjust its frequency and arrive 55.5kHz, electric current to 200mA, then plating piece is suspended to and begins in the electroplating solution that is placed in the ultrasonic cleaning tank to electroplate, the electroplating solution prescription is basic identical with the copper plating solution shown in the table 1 with processing parameter, and the current density that is added on the workpiece is 5A/dm
2During plated film to 510 second with the electric current of ultrasonic generator in 30 seconds gradually (evenly) be reduced to 0, do not adding under the ultransonic state plated film 510 seconds then, subsequently in 30 seconds again with the electric current of ultrasonic generator gradually (evenly) be elevated to 200mA, repeat this technological process, depositing time 180 minutes, thus deposition obtains the lamination plated copper film.This plated film is laminate structure, about 2.5 microns of present embodiment lamination Cu plated film thickness in monolayer, about 50 microns of plated film total thickness.
Present embodiment carries out wear resistance, corrosion resistance nature test to the plating Cu stack membrane for preparing, and has estimated the bonding strength between plated film and the matrix.Test-results shows, electroplates the Cu stack membrane and not only has good wear-resisting, corrosion resistance nature, and present superior film substrate bond strength.
Claims (6)
1. electroplate the Cu stack membrane for one kind, it is characterized in that: this stack membrane is by intermittently introducing ultrasonic signal deposits the Cu plated film on metal base material in the electroplating technology process, the metal copper film that obtains is laminate structure, the thickness in monolayer of copper film is in 0.08～2.5 micrometer range, and total thickness can be adjusted in 3.2 microns～50 micrometer ranges according to the actual requirements.
2. according to the preparation method of the described plating of claim 1 Cu stack membrane, it is characterized in that: be substrate with the metallic substance, by intermittently introducing ultrasonic signal deposition Cu plated film, form the Cu stack membrane in the electroplating technology process, concrete steps are as follows:
(1) greasy dirt on the removal base metal surface cleans in organic solvent for ultrasonic;
(2) acid etching;
(3) washing;
(4) introduce ultrasonic signal, metal refining copper film on base material in the electroplating process discontinuous;
(5) wash and dry up, obtain the stack membrane of Cu.
3. according to the preparation method of the described plating of claim 2 Cu stack membrane, it is characterized in that: in the described step (1), the greasy dirt of removing on the base metal surface is workpiece to be immersed in the trieline organic solution scrub.
4. according to the described preparation method who electroplates the Cu stack membrane of claim 2, it is characterized in that: in the described step (1), cleaning in organic solvent for ultrasonic is workpiece to be put into trieline organic solution cleaned 5～10 minutes by Ultrasonic Cleaners, makes workpiece obtain clean surface.
5. according to the preparation method of the described plating of claim 2 Cu stack membrane, it is characterized in that: in the described step (4), introduce ultrasonic signal in the electroplating process discontinuous and be meant:
At first, be that 100～200mA, ultrasonic frequency are plated film 120～510 seconds under 16.5～55.5kHz at hyperacoustic electric current; Then, the electric current with ultrasonic generator was reduced to 0 gradually by 100～200mA in 30 seconds; Then, do not adding under hyperacoustic state plated film 120～510 seconds; Electric current with ultrasonic generator was elevated to 100～200mA gradually by 0 in 30 seconds again; Constantly repeat aforesaid operations, depositing time is 100～240 minutes, obtains the plating Cu stack membrane that needs.
6. according to the preparation method of the described plating of claim 2 Cu stack membrane, it is characterized in that: in the described step (4), the current density of metal refining copper film process is 1～5A/dm on base material
2
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| US6746590B2 (en) * | 2001-09-05 | 2004-06-08 | 3M Innovative Properties Company | Ultrasonically-enhanced electroplating apparatus and methods |
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