CN105586581A - Method for chemical nickel-plating on surface of cement-based piezoelectric composite - Google Patents

Method for chemical nickel-plating on surface of cement-based piezoelectric composite Download PDF

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CN105586581A
CN105586581A CN201610124942.XA CN201610124942A CN105586581A CN 105586581 A CN105586581 A CN 105586581A CN 201610124942 A CN201610124942 A CN 201610124942A CN 105586581 A CN105586581 A CN 105586581A
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nickel
composite material
solution
cement
plating
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CN105586581B (en
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黄世峰
张颖
徐丽雯
渠娇
徐东宇
程新
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University of Jinan
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University of Jinan
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

The invention discloses a method for chemical nickel-plating on the surface of a cement-based piezoelectric composite. The method comprises the steps of coarsening, reducing, activating and nickel plating. Coarsening is conducted in alkaline coarsening fluid. The applied reducing solution is a sodium borohydride methyl alcohol water solution or a sodium borohydride ethyl alcohol water solution. The applied activating solution is an additive-contained nickel acetate water solution or an additive-contained nickel sulfate water solution. The nickel-plating solution comprises 18-22 g/L of nickel sulfate, 8-16 g/L of trisodium citrate, 26-32 g/L of sodium hypophosphite, 8-14 g/L of sodium acetate and 6-10 g/L of borax, and the pH is 6.5-7.5. The method for chemical nickel-plating on the surface of the cement-based piezoelectric composite is suitable for all kinds of cement-based piezoelectric composites with piezoelectric ceramics as function bodies and cement and epoxy resin as base bodies, the cost is low, and the environmental protection property is better; prepared coatings are flat in surface, uniform, consistent, good in corrosion resistance and electrical conductivity, high in weldability, capable of being closely combined with the cement-based piezoelectric composite, not prone to being disengaged and good in binding force, and application prospects are very good.

Description

A kind of method at cement base piezoelectric composite material chemical nickel plating on surface
Technical field
The present invention relates to a kind of method at cement base piezoelectric composite material plating nickel on surface, be specifically related to a kind of in cement basedPiezo-electricity composite material surface, without the method for palladium salt activating chemical nickel plating, belongs to Chemical Plating of Non metal Material technical field.
Background technology
Piezoelectric, because of its special data-collection characteristic, is widely used in the health monitoring of large scale civil engineering.Piezoelectric mainly comprises piezoelectric ceramics and piezo-electricity composite material. The electromechanical Coupling of piezoelectric ceramics is strong, piezoelectric strain constantHeight, but dielectric constant is higher, so piezoelectric voltage constant is generally lower. And their toughness is poor, fragility cracking, causesDevice reliability by its making is not high, poor durability. Piezo-electricity composite material is to start to rise the new of research the eighties in 20th centuryType piezoelectric, it is using polymer such as epoxy resin, rubber or PVDF as matrix, using piezoelectric ceramics as functive and shapeThe composite becoming. It combines the feature of piezoelectric ceramics and polymer, has the spies such as dielectric constant is little, density is low, good toughnessPoint, but still there are some defects in Polymers piezo-electricity composite material, as not high in the difficulty that polarizes, piezoelectric property, cannot be fineThe health monitoring that is applied to large scale civil engineering in.
Cement base piezoelectric composite material be using the mixture of cement and polymer as matrix material, using piezoelectric ceramics asFunctive material. That cement base piezoelectric composite material has is good with concrete compatibility, intensity is high, good endurance, perception are sensitiveSpend the features such as high and cost is low, its development at the traditional cement-based material of transformation, expand its application and advance all kinds of buildingsEngineering structure has engineering application value widely to intelligent direction development, thereby is more and more subject in field of civil engineeringPeople's attention. But, because this cement base piezoelectric composite material is by cement, polymer, three kinds of different materials of piezoelectric ceramicsMaterial is combined with each other, and cement is Binder Materials, and polymer is that high molecular polymer, piezoelectric ceramics are typical inorganic non-metallicMaterial, mechanical property, surface state and other material after component, technical process, formation mechanism and the formation of three kinds of materialsCharacteristic is all different, if make metal coating have good adhesive strength and reach uniformity on these three kinds of materials simultaneouslyProperty is very difficult, thereby has limited the scope of application of such cement base piezoelectric composite material. Therefore, research is suitable for this typeThe preparation method of cement base piezoelectric composite material electrode, makes cement base piezoelectric composite material bring into play good piezoelectric property, to waterApplying of mud base piezoelectric composite material has very important significance.
Chemical nickel plating, because its coating has good hardness, corrosion resistance, electric conductivity and solderability etc., becomes nonmetallic materialsThe effective means of surface metalation. Traditional chemical plating of non-metal material nickel technique is used PdCl2Carry out acid alligatoring-aciditySensitization-acidic activated-nickel plating technology, this process treatment process more complicated, PdCl2Expensive and there is toxicity, grain is urgedChange activity strong, in chemical plating process, have unavoidably palladium particle to fall into plating solution, affect the stability of plating solution. In addition, palladium salt is livedChange method need be carried out under acid condition, and acid has very strong corrosive effect to cement, therefore the uncomfortable Heshui of palladium salt activation method nickel platingMud base piezoelectric composite material.
At present carry out on cement base piezoelectric composite material surface there is no bibliographical information without the method for palladium salt activating chemical nickel plating,Therefore research and develop a kind of applicable cement base piezoelectric composite material, in alkalescence or neutral medium, carry out alligatoring, sensitization, activationTo avoid the nickel chemical plating technology of the erosion of acid medium to cement base piezoelectric composite material, for cement base piezoelectric composite materialApplication and development and the improvement of nickel chemical plating technology process significant. In addition, use, reduce work to saving noble metalSkill cost is also significant.
Summary of the invention
The object of this invention is to provide a kind of method at cement base piezoelectric composite material chemical nickel plating on surface, the method rootAccording to the feature of cement base piezoelectric composite material, chemical nickel plating method and technological parameter are improved and optimized, the nickel of gainedQuality of coating is good, is combined with cement base piezoelectric composite material.
Before this, inventor has successfully worked out Polymers piezo-electricity composite material plating nickel on surface technique, and declaresPatent, application number is: 201110271920.3. But, because there is very large difference in the self character of cement and polymer,Through verification experimental verification, the method is only suitable for the composite of polymer and piezoelectric ceramics composition, and it is multiple to be not suitable for cement base piezoelectricCondensation material. And the method all needs to use acid in alligatoring, sensitization, activation process, this has very large corrosion to do to cementWith, be more not suitable for cement base piezoelectric composite material. Therefore, inventor is for cement base piezoelectric composite material self-characteristic, logicalExcessive quantity research and experiment have obtained the chemical nickel plating method of applicable cement base piezoelectric composite material, and technological process is: alligatoring-alsoFormer-activation-nickel plating, whole process is all implemented under neutrality or alkali condition, has both effectively avoided acid condition to press cement basedReply the erosion of condensation material by cable, can obtain on cement base piezoelectric composite material surface again well behaved coating.
The said cement base piezoelectric composite material of the present invention, refers to taking piezoelectric ceramics as functive, with polymer and waterThe mixture of mud is the piezo-electricity composite material that matrix forms. Described piezoelectric ceramics can be various disclosed piezoelectric ceramics, for examplePMN-ZT, PZT piezoelectric ceramics; Described cement can be disclosed in prior art, can be used as piezo-electricity composite material matrixVarious cement, for example Portland cement; Described polymer can be disclosed in prior art, can do with cement mixingFor the various polymer of matrix, polymer of the present invention refers in particular to epoxy resin. Cement base piezoelectric composite material of the present invention is passableThe types such as 1-3 type, 0-3 type, 1-1 type. In preparation process, in order to make piezo-electricity composite material moulding good, except piezoelectricity potteryOutside porcelain, cement and polymer, also inevitably there is the auxiliary agent of some assistant formations, such as curing agent, diluent etc. WhenWhen its plating nickel on surface, nickel needs simultaneously and piezoelectric ceramics, cement, polymer three form strong bonded, the nickel electricity obtaining like thisThe utmost point could be combined with cement base piezoelectric composite material well, has greatly increased the difficulty of nickel plating.
The present invention's research has obtained being applicable to the method for above-mentioned cement base piezoelectric composite material chemical nickel plating on surface, the method bagDraw together the step of cement base piezoelectric composite material surface being carried out to alligatoring, reduction, activation, Nickel Plating Treatment, wherein, alligatoring is at alkaline coarseChange in liquid and carry out, the reducing solution used that reduces is the methanol aqueous solution of sodium borohydride or the ethanol water of sodium borohydride, livesChange activating solution used and be the nickel acetate that contains additive or the aqueous solution of nickelous sulfate, nickel plating nickel-plating liquid used consists of: sulphurAcid nickel 18-22g/L, trisodium citrate 8-16g/L, inferior sodium phosphate 26-32g/L, sodium acetate 8-14g/L, borax 6-10g/L,PH is 6.5-7.5.
Further, in the inventive method, be also included in before alligatoring surface is carried out in cement base piezoelectric composite material surfaceThe step of polishing, oil removing.
Further, in the inventive method, alligatoring coarsening solution used is the aqueous solution, and the compound method of coarsening solution is: willNaOH mixes with the mass ratio of 5:1 with sodium carbonate, and what to be made into sodium carbonate and NaOH gross mass mark be 35wt% is water-solubleLiquid then adds potassium permanganate and ethylenediamine in this solution, and making potassium permanganate concentration is that 5g/L, ethylenediamine concentration are 30mL/L, obtains coarsening solution.
Further, alligatoring is carried out under 30 DEG C of left and right. General alligatoring required time is 30min left and right.
Further, the methanol aqueous solution that reducing solution of the present invention is sodium borohydride or ethanol water, the one-tenth of activating solutionBe divided into nickel acetate or nickelous sulfate, additive and water, described additive is KI, lauryl sodium sulfate, ethylenediamine or poly-secondGlycol. The present invention adopts the collocation of sodium borohydride and nickel salt, has produced active nickel (activating a little), the party with sodium borohydride reductionThe activation point that method obtains can distribute at cement base piezoelectric composite material surface uniform, makes in follow-up Ni-Speed the nickel dam can beOn piezoelectric ceramics, cement and polymer, be uniformly distributed, the phenomenon such as can not cause layering, come off, is carrying out smoothly of follow-up nickel platingSolid foundation is provided. Nickel activation has replaced traditional palladium salt activation method, and cost is lower, and the feature of environmental protection is better, and has overcomeThe activation of palladium salt must be used acid cement to be caused to the deficiency of adverse effect. In reduction process, sodium borohydride is in the reducing solutionWhen content is 65-75g/L, effect is better. In activation process, nickel acetate or the nickelous sulfate content in activating solution is 5-55g/LShi Xiaoguo is better, through experimental verification, and when in activating solution, nickel salt concentration is 25-35g/L, nickel plating speed and corrosion resistance of coatingBetter, therefore preferably the concentration of nickel salt is 25-35g/L, and most preferable concentrations is 25g/L.
In the present invention, it is solvent that reducing solution is selected methanol aqueous solution or ethanol water, and it is solvent that activating solution is selected water.The selection of solvent has considerable influence, the uniformity to nickel dam and cement based for the uniformity of activation point, the firmness of activation pointPiezo-electricity composite material also has material impact in conjunction with firmness. The present invention is according to the characteristic of cement base piezoelectric composite material, through excessiveAmount experimental study has obtained required solvent, and in the time that sodium borohydride is dissolved in alcohol solution, gained quality of coating is good. Preferably, in the time that the volume ratio of methyl alcohol or ethanol and water is 1:1, effect is best.
In the inventive method, select sodium borohydride reduction, nickel salt activation, reduction can at room temperature be carried out, and activation canAt 25 DEG C-40 DEG C, preferably under 35 DEG C of left and right, to carry out, temperature is all lower. Reduction and activation within a short period of timeCan complete, general, reduction and activation required time are all in 10min left and right.
Further, in activating solution, the content of additive is 20-30mg/L, and described additive is KI, dodecaneBase sodium sulphate, ethylenediamine or polyethylene glycol, be preferably polyethylene glycol. Experiment showed, and can make activation point minute adding of additiveCloth is more even, makes coating and cement base piezoelectric composite material associativity better, is conducive to improve plating speed, the plated crystal of formationGrow, metallic luster is good, and surface topography is better, can also improve the corrosion resistance of coating. In addition, add after additive, liveIt is more firm that change point is adsorbed on cement base piezoelectric composite material surface, is difficult for coming off in Ni-Speed, can not make nickel-plating liquidBecome to pollute, thereby nickel-plating liquid can repeatedly be reused, improved stability and the service life of nickel-plating liquid, reduced nickel platingThe number of times of liquid post processing, has reduced the pollution of nickel-plating liquid to environment, also greatly reduces cost. Further, add after additive platingThe phosphorus content of layer promotes to some extent, and according to the literature, phosphorus content is relevant with coating corrosion resistance, and phosphorus content is higher, and coating is corrosion-resistantProperty is better. This shows, additive add the corrosion resistance that has also increased coating.
Activated processing forms after activation point, and cement base piezoelectric composite material can carry out Nickel Plating Treatment. The present invention is usedThe nickel-plating liquid aqueous solution that is nickelous sulfate, nickel-plating liquid had both needed to arrange in pairs or groups each other with reducing solution and activating solution, needed again to meet waterThe characteristic of mud base piezoelectric composite material itself, inventor, through large quantity research, has obtained the suitable nickel-plating liquid of the present invention, wherein,Best results when nickel-plating liquid is selected following content: nickelous sulfate 20g/L, trisodium citrate 12g/L, inferior sodium phosphate 30g/L,Sodium acetate 12g/L, borax 8g/L, pH is 6.5-7.5. Nickel-plating liquid pH of the present invention is closely neutral, and good stability is difficult for decomposing, canResting period is long, and near neutral nickel-plating liquid has overcome nickel-plating liquid slant acidity and can cause burn into cement base piezoelectric composite materialThe deficiencies such as nickel-plating liquid meta-alkalescence gained nickel dam quality reduces, plating solution is unstable. In addition, by the cooperation of each component, gainedThe advantages such as coating can reach uniformity, and corrosion-resistant, adhesion is good.
Further, nickel-plating liquid can be adjusted pH with ammoniacal liquor.
Further, nickel plating is carried out 45 DEG C of left and right, for example 45-50 DEG C. Plating time is relevant with the thickness of gained nickel dam,In the time that plating time is 15-20min left and right, nickel layer thickness can reach 2 μ m left and right, and the adjustment time obtains and closes as requiredSuitable thickness. According to the report of prior art, in the nickel-plating liquid of partial neutral, need to be at higher temperature, for example 60-70 DEG CCould carry out preferably nickel plating, and nickel plating temperature of the present invention only needs 45 DEG C of left and right, reduced energy consumption and brought by high temperatureThe defect of the unstable grade of plating solution, this and the present invention handle well early stage, and the activation point of formation is evenly distributed, distribute has compared with high point moreSystem. Under this nickel plating condition, the coating densification of gained, evenly, adhesion is good, good quality.
The method of nickel plating of the present invention, specifically comprises the following steps:
(1) polished and oil removing in cement base piezoelectric composite material surface;
(2) cement base piezoelectric composite material after oil removing is placed in to coarsening solution and carries out roughening treatment, after processing, water rinses;
(3) cement base piezoelectric composite material after alligatoring is put into reducing solution and reduced processing, the cement based after reductionPiezo-electricity composite material is put into activating solution again and is carried out activation processing;
(4) after activation, cement base piezoelectric composite material is taken out, water rinses, and adds in nickel-plating liquid and carries out chemical nickel plating, and coating reachesDuring to desired thickness, stop nickel plating, obtain nickel coating.
The present invention is directed to the acid nonfast particularity of cement base piezoelectric composite material, provide at cement base piezoelectric composite materialSurface is without the chemical nickel plating method of palladium salt activation, and the method is first pre-by mechanical grinding, oil removing, alligatoring, reduction, activation etc. in earlier stageProcessing makes its surface form self-catalysis activated centre, and then carries out chemical nickel plating, and the no acidic reagent of whole Ni-Speed is got involved,Can not cause damage to cement base piezoelectric composite material. The present invention has the following advantages:
1, the present invention utilizes sodium borohydride reduction to produce active nickel at normal temperatures, replaces the activation of palladium salt with nickel activation, science, closesReason, cost is lower, and the feature of environmental protection is better.
2, nickel-plating liquid of the present invention is closely neutral, and good stability is difficult for decomposing, can the resting period long.
3, nickel plating process of the present invention is suitable for various taking piezoelectric ceramics as functive, taking cement and epoxy resin as matrixCement base piezoelectric composite material. Nickel plating is carried out under cryogenic conditions, and energy consumption is low, and repetitive rate is high, by the cooperation of each process conditions,Can on piezoelectric ceramics and cement matrix, plate metal nickel dam, for the subsequent applications of cement base piezoelectric composite material provides simultaneouslyFacility.
4, coating of the present invention is nickel-phosphorus alloy, and coating surface is smooth, and crystal grain is in conjunction with closely and be evenly distributed, coating even oneCause, corrosion resistance is good, good conductivity, solderability are strong, be combined with cement base piezoelectric composite material closely, and difficult drop-off, adhesion is goodGood, there is good application prospect.
Brief description of the drawings
Fig. 1 nickel acetate concentration is on plating fast impact.
Fig. 2 methanol-water is made the SEM figure (3000 times) of solvent gained coating.
Fig. 3 alcohol-water is made the SEM figure (3000 times) of solvent gained coating.
The Ta Feier curve of Fig. 4 nickel acetate and nickelous sulfate activation gained coating.
The SEM of gained coating figure (3000 times) when Fig. 5 additive is KI.
The SEM of gained coating figure (3000 times) when Fig. 6 additive is lauryl sodium sulfate.
The SEM of gained coating figure (3000 times) when Fig. 7 additive is ethylenediamine.
The SEM of gained coating figure (3000 times) when Fig. 8 additive is polyethylene glycol.
The SEM of gained coating figure (3000 times) when Fig. 9 additive is softex kw.
The impact of Figure 10 different additive on deposit in acidic electroless Ni electrolyte.
Figure 11 has palladium activation method gained coating surface SEM+EDS figure.
Figure 12 has palladium activation and no-palladium activating gained coating Ta Feier curve.
The SEM figure (3000 times) of Figure 13 comparative example 2 gained coating.
The SEM figure (3000 times) of Figure 14 comparative example 3 gained coating.
Detailed description of the invention
Below by specific embodiment, the present invention will be further elaborated, and following explanation is only in order to explain thisBright, its content is not limited.
In the inventive method, utilize electrochemical workstation to measure the corrosion resistance of coating, concrete grammar is with 3.5% chlorineChange sodium solution is etchant solution, and taking saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, and corroded area is1.5cm2, sweep speed 0.1V/s, stand-by period 2s.
In the inventive method, utilize weight method to measure the plating speed of coating:
In formula: v is plating speed (gdm-2·h-1); Δ m is the weightening finish (g) of plating piece before and after plating; S is coating area (dm2); T isPlating time (h).
In the inventive method, utilize ESEM to carry out morphology analysis to nickel coating.
In the inventive method, utilize energy depressive spectroscopy to carry out constituent analysis to coating.
In following embodiment, taking 1-3 type cement base piezoelectric composite material as example, introduce in detail Ni-Speed and each technique ginsengNumber changes the impact on nickel plating effect. Cement base piezoelectric composite material used taking PZT-5 piezoelectric ceramics as functive, with ordinary siliconThe mixture of acid salt cement, epoxy resin and curing agent, as matrix, adopts cutting-casting to be prepared from, and epoxy resin canBe various can be for the epoxy resin of piezo-electricity composite material, for example glycidol amine or line style aliphatic category epoxy treeFat, for example AB-grouting resin. Preparation method is: the direction by cutting machine along piezoelectric ceramics polarization, the body shared according to ceramic phaseIntegration number, accurately cuts out the piezoelectric ceramics post of required size successively; Piezoelectric ceramics after adopting supersonic wave cleaning machine to cuttingPiece carries out ultrasonic cleaning, to remove residual foreign material wherein, then the piezoelectric ceramics block after cleaning is dried and is placed in mould;The mass ratio preparation matrix material of pressing cement, epoxy resin and curing agent 4:4:1, vacuumizes processing after fully stirring, andMatrix after treatment is cast in mould, and again vacuumizes processing; Sample is cut and polishing, untilPiezoelectric ceramics post is exposed on sample two surfaces completely; Finally prepare cement base piezoelectric composite material. Gained cement base piezoelectric is compoundMaterial is of a size of 8 × 8mm2, thickness is 2mm.
Embodiment 1
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: cement base piezoelectric composite material surface finish to be plated and oil removing:
By to be plated for cement base piezoelectric composite material 600#, 1000# sand paper polish successively, then use the meticulous polishing of abrasive paper for metallograph, superSound cleans after 10min, is immersed containing ultrasonic cleaning 20min in the degreasing fluid of acetone.
Step 2: cement base piezoelectric composite material surface coarsening to be plated processing:
Cement base piezoelectric composite material after oil removing is placed in to coarsening solution alligatoring, processes 30min at 30 DEG C, then water rinses dryOnly, to remove coarsening solution. The compound method of coarsening solution is: NaOH and sodium carbonate are made into quality with the mass ratio of 5:1 and divideNumber, for the solution (sodium carbonate and NaOH total concentration are 35%) of 35wt%, then adds potassium permanganate and second two in this solutionAmine, potassium permanganate concentration is 5g/L, ethylenediamine concentration is 30mL/L.
Step 3: cement base piezoelectric composite material reduction to be plated is processed:
Cement base piezoelectric composite material after alligatoring is put into reducing solution, at room temperature soak 10min. Reducing solution is:The mixed liquor of sodium borohydride, first alcohol and water, wherein the content of sodium borohydride is 70g/L, the volume ratio of first alcohol and water is 1:1.
Step 4: cement base piezoelectric composite material activation processing to be plated:
By reduction after cement base piezoelectric composite material take out directly immersion activating solution in, at 35 DEG C, soak 10min, make nickel fromSon can be reduced to elemental nickel and be adsorbed on matrix surface, and after activation, water is rinsed well.
Step 5: cement base piezoelectric composite material chemical nickel plating on surface after activation:
Cement base piezoelectric composite material after activation is immersed in nickel-plating liquid and carries out chemical nickel plating, plating 20min. Nickel-plating liquid is:Nickelous sulfate 20g/L, trisodium citrate 12g/L, inferior sodium phosphate 30g/L, sodium acetate 12g/L, borax 8g/L, uses ammoniacal liquorAdjustment pH is 6.5-7.5, and bath temperature is 45 DEG C.
In above-mentioned steps 4, the aqueous solution that activating solution is nickel acetate, carries out repeatedly parallel test, makes nickel acetate in activating solutionContent be respectively 5g/L, 15g/L, 25g/L, 35g/L, 45g/L, 55g/L, the shadow of test nickel acetate content to coatingRing.
Respectively the performance of the coating obtaining under different activation solution concentrations is tested. Gained coating naked eyes under each concentrationSee equal outward appearance light, solderability is all good, and coating surface is all comparatively smooth, fine and close, repeatedly electrode surface is glued with 3M adhesive tapePaste, after pasting, coating is all very complete, and without obviously damaged and come off, each coating and piezo-electricity composite material surface conjunction are all good,In macroscopic view, all do not see the line of demarcation between cement matrix and ceramic matrix at each coating surface.
Nickel acetate concentration is shown in Fig. 1 to plating fast impact, and as can be seen from the figure, nickel plating speed is dense with the main salt nickel acetate of activationThe rising of degree and increasing, within the scope of 5-25g/L time, plates fast amplification comparatively obvious, is almost linear growth, at 25-55g/LIn scope time, although plating speed also has increase with the rising of nickel acetate concentration, amplification slows down.
Nickel acetate concentration has a certain impact to corrosion resistance coating, obtains the corrosion certainly of coating under different nickel acetate concentrationCurrent potential is as shown in table 1, and more just, corrosion resistance of coating is better for corrosion potential, as can be seen from Table 1: along with nickel acetate concentrationIncrease, corrosion potential is shuffled, in the time that nickel acetate concentration is 25-35g/L, and this scope maximum of shuffling, corrosion resistance is best, exceedsThis scope, shuffles and all has and reduce, corrosion resistance variation.
Under the different nickel acetate concentration of table 1, obtain the corrosion potential of coating
Nickel acetate concentration/mgL-1 5 15 25 35 45 55
Ecorr/ V -0.6572 -0.5949 -0.5344 -0.5243 -0.5445 -0.6033
Comprehensive above various performances, all can obtain better coating when nickel acetate content is 5-55g/L, wherein preferred 25-35g/L,Most preferably 25g/L.
Embodiment 2
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: cement base piezoelectric composite material matrix reduction to be plated is processed:
Cement base piezoelectric composite material after alligatoring is put into reducing solution, at room temperature soak 10min.
Step 4: cement base piezoelectric composite material matrix activation processing to be plated:
Cement base piezoelectric composite material after reduction is taken out and immersed in activating solution, at 35 DEG C, soak 10min, make nickel ion energyBe reduced to elemental nickel and be adsorbed on matrix surface, and water is rinsed well. Activating solution is the aqueous solution of nickel acetate, the containing of nickel acetateAmount is 25g/L.
Step 5: with embodiment 1.
In above-mentioned steps 3, reducing solution is respectively methanol aqueous solution or the ethanol water of sodium borohydride, sodium borohydrideContent is 65g/L, and the volume ratio of methyl alcohol or ethanol and water is 1:1.
The scanning electron microscope (SEM) photograph of the coating that employing methanol aqueous solution obtains is shown in Fig. 2, coating surface light, and coating is smooth, crystal grainBetween in conjunction with fine and close, adhesion is good. With 3M adhesive tape, coating surface is pasted repeatedly, result coating surface is obviously not brokenDamage, illustrate that the adhesion of coating is good. Coating is carried out to constituent analysis with energy depressive spectroscopy, cement matrix part phosphorus content reaches6.03wt%, ceramic matrix part phosphorus content reaches 6.76wt%, and deposit in acidic electroless Ni electrolyte is higher, has good corrosion resistance.
The scanning electron microscope (SEM) photograph of the coating that employing ethanol water obtains is shown in Fig. 3, coating surface light, and coating is smooth, crystal grainBetween in conjunction with fine and close, adhesion is good. With 3M adhesive tape, coating surface is pasted repeatedly, result coating surface is obviously not brokenDamage, illustrate that the adhesion of coating is good. Coating is carried out to constituent analysis with energy depressive spectroscopy, cement matrix part phosphorus content reaches4.93wt%, ceramic matrix part phosphorus content reaches 4.39wt%.
Can be found out by Fig. 2 and Fig. 3, the microscopic appearance of the coating that the different reduction of employing solvents obtain is different, adoptsThe coating surface structure cell that methanol aqueous solution obtains is less, and the coating line of demarcation on cement matrix and ceramic matrix is not obvious, adoptsThe coating surface structure cell that ethanol water obtains is larger, and the coating line of demarcation on cement matrix and ceramic matrix is obvious comparatively speakingSome.
In sum, sodium borohydride is made solvent with methanol-water mixed liquor or ethanol water mixed liquid and all can be plated preferablyLayer, uses methanol-water mixed liquor gained deposit in acidic electroless Ni electrolyte higher, and corrosion resistance is better, but the toxicity of use ethanol water mixed liquid moreLow, more environmental protection.
Embodiment 3
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: with embodiment 1.
Step 4: cement base piezoelectric composite material matrix activation processing to be plated:
Cement base piezoelectric composite material after reduction is taken out and immersed in activating solution, at 35 DEG C, soak 10min, make nickel ion energyBe reduced to elemental nickel and be adsorbed on matrix surface, after activation, water is rinsed well.
Step 5: with embodiment 1.
In above-mentioned steps 4, activating solution is the aqueous solution of nickel acetate or nickelous sulfate, and the content of nickel acetate or nickelous sulfate is 25g/L。
The equal surface-brightening of coating that nickel acetate and nickelous sulfate obtain, smooth, intercrystalline is in conjunction with densification. With 3M adhesive tape to coatingPaste repeatedly on surface, and coating surface all, less than obviously damaged, illustrates that the adhesion of coating is good. Nickel acetate and nickelous sulfate instituteThe Ta Feier curve that obtains coating is shown in Fig. 4, and as can be seen from Figure 4, nickelous sulfate activation gained corrosion resistance of coating outline is inferior to nickel acetateActivation gained corrosion resistance of coating, therefore preferred nickel acetate.
Embodiment 4
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: cement base piezoelectric composite material surface finish to be plated and oil removing:
By to be plated for cement base piezoelectric composite material 600#, 1000# sand paper polish successively, then use the meticulous polishing of abrasive paper for metallograph, superSound cleans after 10min, is immersed containing ultrasonic cleaning 20min in the degreasing fluid of acetone.
Step 2: cement base piezoelectric composite material surface coarsening to be plated processing:
Cement base piezoelectric composite material after oil removing is placed in to coarsening solution alligatoring, processes 30min at 30 DEG C, then water rinses dryOnly, to remove coarsening solution. The compound method of coarsening solution is: NaOH and sodium carbonate are made into quality with the mass ratio of 5:1 and divideNumber, for the solution (sodium carbonate and NaOH total concentration are 35%) of 35wt%, then adds potassium permanganate and second two in this solutionAmine, potassium permanganate concentration is 5g/L, ethylenediamine concentration is 30mL/L.
Step 3: cement base piezoelectric composite material reduction to be plated is processed:
Cement base piezoelectric composite material after alligatoring is put into reducing solution, at room temperature soak 10min. Reducing solution is:The mixed liquor of sodium borohydride, first alcohol and water, wherein the content of sodium borohydride is 75g/L, the volume ratio of first alcohol and water is 1:1.
Step 4: cement base piezoelectric composite material activation processing to be plated:
By reduction after cement base piezoelectric composite material take out directly immersion activating solution in, at 35 DEG C, soak 10min, make nickel fromSon can be reduced to elemental nickel and be adsorbed on matrix surface, and after activation, water is rinsed well. Activating solution is the aqueous solution of nickel acetate, secondThe content of acid nickel is 25g/L.
Step 5: with embodiment 1.
Gained coating naked eyes are seen surface-brightening, and solderability is good, and coating surface is comparatively smooth, fine and close, piezoelectric ceramics base and waterBetween mud base, without line of demarcation and crack, repeatedly electrode surface is pasted with 3M adhesive tape, after pasting, coating is still very complete, without brightShow damaged and come off, coating is combined well with base material. Coating is carried out to constituent analysis, cement matrix part phosphorus with energy depressive spectroscopyContent reaches 5.01wt%, and ceramic matrix part phosphorus content reaches 5.59wt%.
Embodiment 5
In the nickel plating of cement base piezoelectric composite material matrix surface, different according to the method for embodiment 4: activation temperature is 25 DEG CWith 40 DEG C.
The equal surface-brightening of gained coating, smooth under 25 DEG C and 40 DEG C of activation temperatures, intercrystalline is in conjunction with densification. With 3M adhesive tape pairCoating surface is pasted repeatedly, and coating surface all, less than obviously damaged, illustrates that the adhesion of coating is good. Use energy depressive spectroscopyCoating is carried out to constituent analysis, and the cement matrix part phosphorus content of gained coating reaches 4.35wt%, ceramic matrix part at 25 DEG CPhosphorus content reaches 4.87wt%. At 40 DEG C, the cement matrix part phosphorus content of gained coating reaches 4.98wt%, ceramic matrix partPhosphorus content reaches 5.64wt%.
Embodiment 6
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: with embodiment 1.
Step 4: cement base piezoelectric composite material activation processing to be plated:
Cement base piezoelectric composite material after reduction is taken out and immersed in different activating solutions, at 35 DEG C, soak 10min, make nickelIon can be reduced to elemental nickel and be adsorbed on matrix surface, and water is rinsed well.
Step 5: with embodiment 1.
In above-mentioned steps 4, activating solution is the nickel acetate aqueous solution of admixture different additive, and additive therefor is respectively iodatePotassium, lauryl sodium sulfate, ethylenediamine, polyethylene glycol, softex kw. In activating solution, the content of nickel acetate is equalFor 25g/L, the content of additive is 30mg/L, does blank with the coating of additive-free activating solution gained simultaneously.
Add after different additives, gained coating is seen obviously boundary of nothing between cement based and piezoelectric ceramics base from naked eyes,Coating is an entirety. Fig. 5 is in activating solution, to add KI, lauryl sodium sulfate, ethylenediamine, polyethylene glycol, 16 to Fig. 9When alkyl trimethyl ammonium bromide, the SEM of coating figure, as can be seen from the figure, adds the equal surface light of coating of different additive gainedBright, smooth, intercrystalline is in conjunction with densification. With 3M adhesive tape, coating surface is pasted repeatedly, coating surface is all damaged less than obvious,The adhesion that coating is described is good.
Figure 10 is the deposit in acidic electroless Ni electrolyte contrast that adds different additive gained in activating solution, as can be seen from the figure, addsAfter KI, lauryl sodium sulfate, ethylenediamine, polyethylene glycol, deposit in acidic electroless Ni electrolyte has raising in various degree, and additive is describedAdd the corrosion resistance that has increased coating, wherein add after polyethylene glycol, cement matrix part phosphorus content reaches 9.97wt%,Ceramic matrix part phosphorus content reaches 10.45wt%, and synergistic effect is the most obvious. And add after softex kw platingThe phosphorus content of layer reduces, and corrosion resistance reduces. This shows, add KI, lauryl sodium sulfate, ethylenediamine, poly-After ethylene glycol, coating intercrystalline is in conjunction with closely, coating morphology be improved significantly, add polyethylene glycol after coating morphology improveSignificantly, add softex kw poor effect.
Embodiment 7
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 4.
Step 2: with embodiment 4.
Step 3: with embodiment 4.
Step 4: with embodiment 4.
Step 5: cement base piezoelectric composite material chemical nickel plating on surface after activation:
Cement base piezoelectric composite material after activation is immersed in nickel-plating liquid and carries out chemical nickel plating, plating 20min. Nickel-plating liquid is:Nickelous sulfate 18g/L, trisodium citrate 8g/L, inferior sodium phosphate 26g/L, sodium acetate 8g/L, borax 6g/L, adjusts with ammoniacal liquorPH is 6.5-7.5,45 DEG C of plating temperatures.
Gained coating surface light, solderability is good, and coating surface is comparatively smooth, fine and close, uses 3M adhesive tape repeatedly to coating tableFace is pasted, and after pasting, coating is still very complete, and without obviously damaged and come off, coating is combined well with base material. Divide by power spectrumAnalyse instrument coating is carried out to constituent analysis, cement matrix part phosphorus content reaches 4.84wt%, and ceramic matrix part phosphorus content reaches5.31wt%。
Comparative example 1
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: cement base piezoelectric composite material sensitization processing to be plated:
Cement base piezoelectric composite material after alligatoring is put into sensitized solution, at room temperature soak 7min. Sensitizing solution formula: chlorineChange sub-tin: 30g/L, 37% concentrated hydrochloric acid: 50mL/L.
Step 4: cement base piezoelectric composite material activation processing to be plated:
Cement base piezoelectric composite material after sensitization is put into activated solution, under room temperature, soak 8min, activating solution formula: chlorinationPalladium: 0.4g/L, 37% concentrated hydrochloric acid: 9.9mL/L.
Step 5: with embodiment 1.
Adopt acidity to have palladium activation method gained coating surface darker, not exclusively, the visible open defect of naked eyes, and plating speed isLittle, Figure 11 is gained coating surface ESEM and energy spectrogram, can find out that by scintigram coating surface is inhomogeneous, has largerCrystal grain is reunited, and by finding out by spectrogram, contain the impurity such as Si, C, O, and phosphorus content is lower, only has 1.54wt%, this in coatingMay be because cement matrix has suffered erosion under acid condition, occur to react with acid, therefore adopt and have palladium activation method instituteObtain coating performance poor.
Figure 12 is the Ta Feier curve comparison figure that has palladium activation and no-palladium activating gained coating, as seen from the figure, adopts without palladiumThe corrosion potential of activation method gained coating is obviously greater than the corrosion potential that has palladium activation method gained coating, and no-palladium activating is describedMethod is more suitable for cement base piezoelectric composite material chemical nickel plating on surface.
Comparative example 2
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: cement base piezoelectric composite material reduction to be plated is processed:
Cement base piezoelectric composite material after alligatoring is put into reducing solution, at room temperature soak 10min, reducing solution is boronThe pure methanol solution of sodium hydride, the content of sodium borohydride is 70g/L.
Step 4: with embodiment 1.
Step 5: with embodiment 1.
Adopt pure methyl alcohol to be easy to volatilization as sodium borohydride solvent, not easy to operate, gained coating and basal body binding force are poor,This may be that the activity of sodium borohydride in pure methyl alcohol is larger, forms more active centre make excessive the making of plating speed at matrix surfaceBecome, from naked eyes, coating surface is inhomogeneous, and cement matrix and ceramic matrix exist crack, and Figure 13 is coating surface morphology figure,By also finding out in figure that coating surface is inhomogeneous, there is larger crystal grain to reunite, the crack in cement matrix and ceramic matrix is larger,Do not covered by coating, therefore adopt pure methyl alcohol to make sodium borohydride solvent and can not obtain well behaved coating.
Comparative example 3
To above-mentioned 8 × 8mm2, nickel plating is carried out on the cement base piezoelectric composite material surface that thickness is 2mm, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: with embodiment 1.
Step 4: with embodiment 1.
Step 5: cement base piezoelectric composite material chemical nickel plating on surface after activation:
Cement base piezoelectric composite material after activation is immersed in nickel-plating liquid and carries out chemical nickel plating, plating 20min. Nickel-plating liquid is:Nickelous sulfate 30g/L, trisodium citrate 20g/L, inferior sodium phosphate 20g/L, sodium acetate 12g/L, borax 8g/L, adjusts with ammoniacal liquorWhole pH is 6.5-7.5, and plating temperature is 45 DEG C.
As shown in figure 14, as seen from the figure, coating surface is inhomogeneous, out-of-flatness, and cement matrix for gained coating surface morphologyExist larger crystal grain pile up and reunite with ceramic matrix intersection. In addition, the adhesion of coating is also poor, repeatedly right with 3M adhesive tapeCoating surface is pasted, and after pasting, coating surface has breakage and obscission. Therefore the selection of nickel-plating liquid is for the property of coatingCan there is considerable influence.
Cannot be exhaustive for embodiments of the present invention, above example is only that part embodiment of the present invention is listed asLift and explanation, on the basis of above embodiment, the kind, the change piezoelectricity that change piezoelectric ceramics, epoxy resin and cement are compoundThe type of material also can obtain effective coating.

Claims (10)

1. in a method for cement base piezoelectric composite material chemical nickel plating on surface, comprise cement base piezoelectric composite material surfaceThe step of carrying out alligatoring, reduction, activation, Nickel Plating Treatment, is characterized in that: alligatoring is carried out in alkaline coarsening solution, reduces usedReducing solution is the methanol aqueous solution of sodium borohydride or the ethanol water of sodium borohydride, activates activating solution used and adds for containingAdd the nickel acetate aqueous solution or the nickel sulfate solution of agent, nickel plating nickel-plating liquid used consists of: nickelous sulfate 18-22g/L, citric acidTrisodium 8-16g/L, inferior sodium phosphate 26-32g/L, sodium acetate 8-14g/L, borax 6-10g/L, pH is 6.5-7.5.
2. method according to claim 1, is characterized in that: described cement base piezoelectric composite material refer to taking piezoelectric ceramics asFunctive, the piezo-electricity composite material forming as matrix taking the mixture of epoxy resin and cement.
3. method according to claim 1 and 2, is characterized in that: the compound method of coarsening solution is: by NaOH and carbonic acidSodium mixes with the mass ratio of 5:1, is made into the aqueous solution that sodium carbonate and NaOH gross mass mark are 35wt%, then molten to thisIn liquid, add potassium permanganate and ethylenediamine, making potassium permanganate concentration is that 5g/L, ethylenediamine concentration are 30mL/L, obtains coarsening solution.
4. method according to claim 1, is characterized in that: in reducing solution, the content of sodium borohydride is 65-75g/L.
5. method according to claim 1, is characterized in that: in reducing solution, the volume ratio of methyl alcohol or ethanol and water is 1:1。
6. method according to claim 1, is characterized in that: the composition of activating solution be nickel acetate or nickelous sulfate, additive andWater, described additive is KI, lauryl sodium sulfate, ethylenediamine or polyethylene glycol.
7. according to the method described in claim 1 or 6, it is characterized in that: in activating solution, the content of nickel acetate or nickelous sulfate is 5-55G/L, is preferably 25-35g/L, most preferably is 25g/L; The content of additive is 20-30mg/L.
8. method according to claim 1, is characterized in that: alligatoring is carried out at 30 DEG C; Reduction is at room temperature carried out; ActivationAt 25 DEG C-40 DEG C, carry out, preferably at 35 DEG C, carry out; Nickel plating is carried out at 45-50 DEG C, preferably at 45 DEG C, carries out.
9. according to the method described in claim 1 or 8, it is characterized in that: coarsening time is 30min, the time of reduction and activation is equalFor 10min.
10. method according to claim 1, is characterized in that, comprises the following steps:
(1) polished and oil removing in cement base piezoelectric composite material surface;
(2) cement base piezoelectric composite material after oil removing is placed in to coarsening solution and carries out roughening treatment, after processing, water rinses;
(3) cement base piezoelectric composite material after alligatoring is put into reducing solution and reduced processing, the cement based after reductionPiezo-electricity composite material is put into activating solution again and is carried out activation processing;
(4) after activation, cement base piezoelectric composite material is taken out, water rinses, and adds in nickel-plating liquid and carries out chemical nickel plating, and coating reachesDuring to desired thickness, stop nickel plating, obtain nickel coating.
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