CN105801172A - Method for preparing cement-based piezoelectric composite material surface nickel electrode - Google Patents
Method for preparing cement-based piezoelectric composite material surface nickel electrode Download PDFInfo
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- CN105801172A CN105801172A CN201610124909.7A CN201610124909A CN105801172A CN 105801172 A CN105801172 A CN 105801172A CN 201610124909 A CN201610124909 A CN 201610124909A CN 105801172 A CN105801172 A CN 105801172A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
- C04B41/69—Metals
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Abstract
The invention discloses a method for preparing a cement-based piezoelectric composite material surface nickel electrode. The method comprises the following steps: roughening, reducing, activating, and plating nickel, wherein the step of roughening is implemented in an alkali roughening liquid; a used reduction solution is a methanol or ethanol solution of sodium borohydride; a used activating liquid is an aqueous solution of nickel acetate or nickel sulfate; a nickel plating liquid consists of 18-22g/L of nickel sulfate, 8-16g/L of trisodium citrate, 26-32g/L of sodium hypophosphite, 8-14g/L of sodium acetate and 6-10g/L of borax, and the pH value is 6.5-7.5. The method is applicable to various cement-based piezoelectric composite materials which take piezoelectric ceramic as a functional body and cement and epoxy resin as substrates, the materials are relatively low in cost and relatively good in environmental friendliness, and an obtained plated layer is smooth in surface, uniform and accordant, good in corrosion resistance, good in conductivity and good in weldability, can be solidly combined with the cement-based piezoelectric composite material, and is not easy to drop, good in binding force and very good in application prospect.
Description
Technical field
The present invention relates to the preparation method of a kind of cement base piezoelectric composite material surface nickel electrode, belong 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 includes piezoelectric ceramics and piezo-electricity composite material.The electromechanical Coupling of piezoelectric ceramics is strong, piezoelectric strain constant
Height, but dielectric constant is higher, so piezoelectric voltage constant is the most relatively low.And they toughness are poor, fragility cracking, cause
The device reliability made by it is the highest, poor durability.Piezo-electricity composite material is to start the eighties in 20th century to rise the new of research
Type piezoelectric, it is using polymer such as epoxy resin, rubber or PVDF as matrix, the shape using piezoelectric ceramics as functive
The composite become.It combines the feature of piezoelectric ceramics and polymer, has the spies such as dielectric constant is little, density is low, good toughness
Point, but polymer base piezoelectric composite material still suffers from some defects, as the most high in polarization difficulty, piezoelectric property, it is impossible to very well
The health monitoring being 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 as
Functive material.Cement base piezoelectric composite material have good with the concrete compatibility, intensity is high, good endurance, perception are sensitive
The features such as degree height and low cost, its development is being transformed conventional cement sill, is being expanded its application and advance all kinds of building
Engineering structure has engineer applied meaning widely to intelligent direction development, thus is more and more subject in field of civil engineering
The attention of people.But, owing to this cement base piezoelectric composite material is by cement, polymer, three kinds of different materials of piezoelectric ceramics
Material is combined with each other, and cement is Binder Materials, polymer be high molecular polymer, piezoelectric ceramics be typical inorganic non-metallic
Material, mechanical property, apparent condition and other material after the component of three kinds of materials, technical process, Forming Mechanism and formation
Characteristic is the most different, if make metal coating have good adhesive strength on these three material and reach uniformity simultaneously
Property is extremely difficult, thus limits the range of such cement base piezoelectric composite material.Therefore, research is suitable for this type
The preparation method of cement base piezoelectric composite material electrode, makes cement base piezoelectric composite material play excellent piezoelectric property, to water
The popularization and application of mud base piezoelectric composite material have very important significance.
Nickel electrode is common electrode, and the chemical nickel plating hardness good because its coating has, corrosion resistance, electric conductivity and solderable
Property etc., become effective means prepared by non-metal material surface nickel electrode.Traditional chemical plating of non-metal material nickel technique uses
PdCl2Carrying out acid roughening-acid sensitization-acidic activated-nickel plating technology, this process treatment process is more complicated, PdCl2Valency
Lattice are expensive and have toxicity, and grain catalysis activity is strong, has palladium granule to fall in plating solution unavoidably, affect the steady of plating solution in plating process
Qualitative.In addition, palladium salt activation method need to be carried out in acid condition, and acid has the strongest corrosive effect to cement, therefore palladium
Salt activation method nickel plating is not suitable for cement base piezoelectric composite material.
Carry out on cement base piezoelectric composite material surface at present there is no document report without the method for palladium salt activating chemical nickel plating,
Therefore research and develop a kind of applicable cement base piezoelectric composite material, carry out being roughened in alkalescence or neutral medium, sensitization, activation
To avoid the acid medium nickel chemical plating technology to the erosion of cement base piezoelectric composite material, for cement base piezoelectric composite material
Application and development and the improvement of nickel chemical plating technology process significant.In addition, to saving noble metal use, reducing work
Skill cost is the most significant.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of cement base piezoelectric composite material surface nickel electrode, the method root
According to the feature of cement base piezoelectric composite material, chemical nickel plating method is used to prepare nickel electrode, by chemical nickel plating method and work
The improvement of skill parameter and optimization, the nickel coating quality of gained is good, is combined with cement base piezoelectric composite material.
Before this, inventor the most successfully works out polymer base piezoelectric composite material plating nickel on surface technique, and declares
Patent, Application No.: 201110271920.3.But, because there is the biggest difference in the self character of cement and polymer,
Experiment proves that, the method is appropriate only for polymer and the composite of piezoelectric ceramics composition, is not appropriate for cement base piezoelectric multiple
Condensation material.Further, the method is required for using acid in roughening, sensitization, activation process, and cement is had the biggest corrosion to make by this
With, it is less suitable for cement base piezoelectric composite material.Therefore, inventor is for cement base piezoelectric composite material self-characteristic, logical
Crossing numerous studies and test the chemical nickel plating method having obtained applicable cement base piezoelectric composite material, technological process is: roughening-and also
Former-activation-nickel plating, whole process is implemented the most under neutral or basic conditions, both effectively prevent acid condition to cement based pressure
The erosion of composite, can obtain again coating of good performance on cement base piezoelectric composite material surface.
Cement base piezoelectric composite material described in the present invention, refers to piezoelectric ceramics as functive, with polymer and water
The mixture of mud is the piezo-electricity composite material that matrix is formed.Described piezoelectric ceramics can be various disclosed piezoelectric ceramics, such as
PMN-ZT, PZT piezoelectric ceramics；Described cement can be disclosed in prior art, can be as piezo-electricity composite material matrix
Various cement, such as Portland cement；Described polymer can be disclosed in prior art, it is possible to makees with cement mixing
For the various polymer of matrix, the present invention refers in particular to epoxy resin.Cement base piezoelectric composite material of the present invention can be 1-3
The types such as type, 0-3 type, 1-1 type.In preparation process, in order to make piezo-electricity composite material molding good, except piezoelectric ceramics, water
Outside mud and polymer, the most inevitably there is the auxiliary agent of some assistant formations, such as firming agent, diluent etc..When at its table
During the nickel plating of face, nickel needs simultaneously and piezoelectric ceramics, cement, polymer three form strong bonded, and the nickel electrode so obtained is
Can be well combined with cement base piezoelectric composite material, considerably increase the difficulty of nickel plating.
Present invention research has obtained the chemical plating method of the surface nickel electrode being suitable for above-mentioned cement base piezoelectric composite material, should
Method includes being roughened cement base piezoelectric composite material surface, reduces, activates, the step of Nickel Plating Treatment, and wherein, roughening exists
Carrying out in alkalescence coarsening solution, the reducing solution used by reduction is that the ethanol of the methanol aqueous solution of sodium borohydride or sodium borohydride is water-soluble
Liquid, the activating solution used by activation is the aqueous solution of nickel acetate or nickel sulfate, and the nickel-plating liquid used by nickel plating consists of: nickel sulfate 18-
22g/L, trisodium citrate 8-16g/L, sodium hypophosphite 26-32g/L, sodium acetate 8-14 g/L, Borax 6-10g/L, pH are
6.5-7.5。
Further, in the inventive method, before being additionally included in roughening, cement base piezoelectric composite material surface is carried out surface
Polishing, the step of oil removing.
Further, in the inventive method, the coarsening solution used by roughening is aqueous solution, and the compound method of coarsening solution is: will
Sodium hydroxide mixes with the mass ratio of 5:1 with sodium carbonate, is made into sodium carbonate and sodium hydroxide total mass fraction is the water-soluble of 35wt%
Liquid, then adds potassium permanganate and ethylenediamine in this solution, and to make potassium permanganate concentration be 5g/L, ethylenediamine concentration is 30mL/
L, obtains coarsening solution.
Further, roughening is carried out under about 30 DEG C.General roughening required time is about 30min.
The present invention uses the collocation of sodium borohydride and nickel salt, has produced active nickel (i.e. activating a little) with sodium borohydride reduction,
The activation point that the method obtains can be uniformly distributed on cement base piezoelectric composite material surface, makes nickel dam energy in follow-up Ni-Speed
Enough it is uniformly distributed on piezoelectric ceramics, cement and polymer, does not results in layering, the phenomenon such as come off, smooth for follow-up nickel plating
Carry out providing solid foundation.Nickel activation instead of traditional palladium salt activation method, and cost is lower, and the feature of environmental protection is more preferable, and gram
Take the deficiency that palladium salt activation must use acid to adversely affect cement.In reduction process, sodium borohydride is at reducing solution
In content when being 65-75 g/L effect preferable.In activation process, nickel salt is nickel acetate or nickel sulfate, nickel acetate or nickel sulfate
When content in activating solution is 5-55 g/L, effect is preferable, and in experimental verification, activating solution, nickel salt concentration is 25-35g/L
Time, nickel plating speed and corrosion resistance of coating are preferable, and therefore the concentration of preferred nickel salt is 25-35g/L, and most preferable concentrations is 25g/
L。
In the present invention, reducing solution selects methanol aqueous solution or ethanol water to be solvent, and activating solution selects water to be solvent.
The select uniformity for activation point, the firmness of activation point of solvent have considerable influence, uniformity and the cement based to nickel dam
Piezo-electricity composite material degree of being firmly combined with also has a major impact.The present invention is according to the characteristic of cement base piezoelectric composite material, through excessive
Amount experimentation has obtained required solvent, and when sodium borohydride is dissolved in alcohol-water solution, gained quality of coating is good.Preferably
, when the volume ratio of methanol or ethanol and water is 1:1, effect is best.
In the inventive method, selecting the activation of sodium borohydride reduction, nickel salt, reduction can at room temperature carry out, activate permissible
Carrying out at 25 DEG C-40 DEG C, preferably carry out under about 35 DEG C, temperature is the most relatively low.Reduce and activate within a short period of time
Can complete, general, reduce and activate required time all at about 10min.
After activated process forms activation point, cement base piezoelectric composite material can carry out Nickel Plating Treatment.Used by the present invention
The aqueous solution that nickel-plating liquid is nickel sulfate, nickel-plating liquid had both needed to arrange in pairs or groups each other with reducing solution and activating solution, and had needed again to meet water
The characteristic of mud base piezoelectric composite material itself, inventor, through numerous studies, has obtained the suitable nickel-plating liquid of the present invention, wherein,
Best results during nickel-plating liquid selection following content: nickel sulfate 20g/L, trisodium citrate 12g/L, sodium hypophosphite 30g/L,
Sodium acetate 12 g/L, Borax 8g/L, pH are 6.5-7.5.Nickel-plating liquid pH weakly acidic pH of the present invention, good stability, it is not easily decomposed, can
Resting period is long, and the nickel-plating liquid of weakly acidic pH overcomes nickel-plating liquid slant acidity and cement base piezoelectric composite material can be caused burn into
The deficiencies such as nickel-plating liquid meta-alkalescence gained nickel dam quality reduces, plating solution is unstable.Additionally, by the cooperation of each component, gained
Coating can reach uniformity, the advantages such as corrosion-resistant, adhesion is good.
Further, nickel-plating liquid can adjust pH with ammonia.
Further, nickel plating is carried out at about 45 DEG C, such as 45-50 DEG C.Plating time is relevant with the thickness of gained nickel dam,
When plating time is about 15-20min, nickel layer thickness can reach about 2 m, and the time that can adjust as required obtains closes
Suitable thickness.According to the report of prior art, in the nickel-plating liquid of partial neutral, need at a higher temperature, such as 60-70 DEG C
Could preferably carry out nickel plating, and nickel plating temperature of the present invention only needs about 45 DEG C, reduce energy consumption and brought by high temperature
The defect that plating solution is unstable etc., this handles well with early stage of the present invention, and the activation point of formation is evenly distributed, be distributed and have relatively high point more
System.Under the conditions of this nickel plating, the plated layer compact of gained, uniformly, adhesion good, good quality.
The preparation method of nickel electrode of the present invention, specifically includes following steps:
(1) carry out polishing and oil removing by cement base piezoelectric composite material surface；
(2) being placed in coarsening solution by the cement base piezoelectric composite material after oil removing and carry out roughening treatment, after process, water rinses；
(3) cement base piezoelectric composite material after being roughened is put into and is carried out reduction treatment in reducing solution, the cement based after reduction
Piezo-electricity composite material places into and carries out activation processing in activating solution；
(4) after activation, being taken out by cement base piezoelectric composite material, water rinses, and adds in nickel-plating liquid and carries out chemical nickel plating, and coating reaches
To stopping nickel plating during desired thickness, obtain nickel coating, namely nickel electrode.
The present invention is directed to the acid nonfast particularity of cement base piezoelectric composite material, it is provided that at cement base piezoelectric composite material
The chemical nickel plating method that surface activates without palladium salt, the method first pass through early stage mechanical grinding, oil removing, be roughened, reduce, activation etc. pre-
Process makes its surface form autocatalytic activity center, carries out chemical nickel plating the most again, and the no acidic reagent of whole Ni-Speed is got involved,
Cement base piezoelectric composite material will not be caused damage.The invention have the advantages that
1, the present invention utilizes sodium borohydride reduction to produce active nickel at normal temperatures, replaces palladium salt activation, science, conjunction with nickel activation
Reason, cost is relatively low, and the feature of environmental protection is more preferable.
2, nickel-plating liquid weakly acidic pH of the present invention, good stability, be not easily decomposed, can the resting period long.
3, nickel electrode preparation method of the present invention is suitable for various with piezoelectric ceramics as functive, with cement and epoxy resin be
The cement base piezoelectric composite material of matrix.Nickel plating is carried out under cryogenic, and energy consumption is low, and repetitive rate is high, by each process conditions
Cooperation, it is possible on piezoelectric ceramics and cement matrix, plate metal nickel dam, follow-up for cement base piezoelectric composite material simultaneously
Application is provided convenience.
4, coating of the present invention is nickel-phosphorus alloy, and coating surface is smooth, and crystal grain is tightly combined and is evenly distributed, coating uniform one
Causing, corrosion resistance is good, good conductivity, solderability strong, is tightly combined with cement base piezoelectric composite material, difficult drop-off, and adhesion is good
Good, there is good application prospect.
Accompanying drawing explanation
The impact on plating speed of Fig. 1 nickel acetate concentration.
Fig. 2 methanol-water makees SEM figure (3000 times) of solvent gained coating.
Fig. 3 alcohol-water makees SEM figure (3000 times) of solvent gained coating.
Fig. 4 nickel acetate and the Tafel curve of nickel sulfate activation gained coating.
Fig. 5 has palladium activation method gained coating surface SEM+EDS to scheme.
Fig. 6 has palladium activation and no-palladium activating gained coating Tafel curve.
SEM figure (3000 times) of Fig. 7 comparative example 2 gained coating.
SEM figure (3000 times) of Fig. 8 comparative example 3 gained coating.
Detailed description of the invention
Below by specific embodiment, the present invention will be further elaborated, and the description below is merely to explain this
Bright, its content is not defined.
In the inventive method, utilizing electrochemical workstation to measure the corrosion resistance of coating, concrete grammar is with 3.5% chlorine
Change sodium solution is etchant solution, and with saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, and corroded area is
1.5cm2, scanning speed 0.1 V/s, waiting time 2 s.
In the inventive method, the plating utilizing weight method mensuration coating is fast:
In formula: v is plating speed (g dm-2·h-1)；Δ m is the weightening finish (g) of plating piece before and after plating；S is plate areas (dm2)；T is
Plating time (h).
In the inventive method, utilize scanning electron microscope that nickel coating is carried out morphology analysis.
In the inventive method, utilize energy depressive spectroscopy that coating is carried out component analysis.
In following embodiment, as a example by 1-3 type cement base piezoelectric composite material, Ni-Speed and each technique ginseng are discussed in detail
The number change impact on nickel plating effect.Cement base piezoelectric composite material used is with PZT-5 piezoelectric ceramics as functive, with ordinary silicon
The mixture of acid salt cement, epoxy resin and firming agent, as matrix, uses cutting-casting to be prepared from, and epoxy resin can
To be the various epoxy resin that may be used for piezo-electricity composite material, such as (+)-2,3-Epoxy-1-propanol amine or linear aliphatic class asphalt mixtures modified by epoxy resin
Fat, such as AB-is in the milk resin.Preparation method is: the direction polarized along piezoelectric ceramics by cutting machine, according to the body shared by ceramic phase
Fraction, the most accurately cuts out the piezoelectric ceramics post of required size；Use ultrasonic washing unit to the piezoelectric ceramics after cutting
Block carries out ultrasonic cleaning, and to remove residual foreign material therein, the piezoelectric ceramics block after then cleaning dries and is placed in mould；
By cement, epoxy resin and the mass ratio preparation matrix material of firming agent 4:4:1, after being sufficiently stirred for, carry out evacuation process, and
Matrix after processing is cast in mould, and again carries out evacuation process；Carry out cutting and polishing by sample, until
Sample two surface is completely exposed piezoelectric ceramics post；Finally prepare cement base piezoelectric composite material.Gained cement base piezoelectric is combined
The size of material is 8 × 8mm2, thickness is 2mm.
Embodiment 1
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, and step is as follows:
Step 1: cement base piezoelectric composite material surface to be plated polishing and oil removing:
Cement base piezoelectric composite material 600#, 1000# sand paper to be plated is polished successively, more finely polishes with abrasive paper for metallograph, super
After sound cleans 10min, it is dipped in the degreasing fluid containing acetone ultrasonic cleaning 20min.
Step 2: cement base piezoelectric composite material surface coarsening to be plated processes:
Cement base piezoelectric composite material after oil removing is placed in coarsening solution roughening, processes 30min at 30 DEG C, then rinse with water dry
Only, to remove coarsening solution.The compound method of coarsening solution is: with the mass ratio of 5:1, sodium hydroxide is made into quality with sodium carbonate and divides
Number is the solution (sodium carbonate and sodium hydroxide total concentration are 35%) of 35wt%, then adds potassium permanganate and second two in this solution
Amine, potassium permanganate concentration is 5g/L, and ethylenediamine concentration is 30mL/L.
Step 3: cement base piezoelectric composite material reduction treatment to be plated:
Cement base piezoelectric composite material after roughening is put in reducing solution, at room temperature soaks 10min.Reducing solution is:
Sodium borohydride, the mixed liquor of first alcohol and water, wherein the content of sodium borohydride is 70 g/L, and the volume ratio of first alcohol and water is 1:1.
Step 4: cement base piezoelectric composite material activation processing to be plated:
Will reduction after cement base piezoelectric composite material take out be directly immersed in activating solution, at 35 DEG C soak 10min, make nickel from
Son can be reduced to elemental nickel absorption and rinse well with water after matrix surface, activation.
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:
Nickel sulfate 20g/L, trisodium citrate 12g/L, sodium hypophosphite 30g/L, sodium acetate 12 g/L, Borax 8g/L, use ammonia
Adjustment pH is 6.5-7.5, and bath temperature is 45 DEG C.
In above-mentioned steps 4, activating solution is the aqueous solution of nickel acetate, carries out repeatedly parallel test, makes nickel acetate in activating solution
Content be respectively 5 g/L, 15 g/L, 25 g/L, 35 g/L, 45 g/L, 55 g/L, test the nickel acetate content shadow to coating
Ring.
Respectively the performance of the coating obtained under different activation solution concentrations is tested.Gained coating naked eyes under each concentration
Seeing equal shiny appearance, solderability is the best, and coating surface is the most smooth, fine and close, repeatedly glues electrode surface with 3M adhesive tape
Patch, after stickup, coating is the most complete, and nothing is the most damaged and comes off, and each coating is combined all good with piezo-electricity composite material surface,
Macroscopically all do not see the demarcation line between cement matrix and ceramic matrix at each coating surface.
The impact of plating speed is shown in Fig. 1 by nickel acetate concentration, it can be seen that nickel plating speed is dense with activating main salt nickel acetate
The rising of degree and increase, time in the range of 5-25 g/L, plating speed amplification is more obvious, the most linearly increases, at 25-55 g/L
In the range of time, although plating speed also has increase with the rising of nickel acetate concentration, but amplification slows down.
Corrosion resistance coating is had a certain impact by nickel acetate concentration, obtains the corrosion certainly of coating under different nickel acetate concentration
Current potential is as shown in table 1, and the most just, corrosion resistance of coating is the best, as can be seen from Table 1 for corrosion potential: along with nickel acetate concentration
Increasing, corrosion potential is shuffled, and when nickel acetate concentration is 25-35g/L, this scope is shuffled maximum, and corrosion resistance is best, exceeds
This scope, shuffles and all has reduction, and corrosion resistance is deteriorated.
The corrosion potential of coating is obtained under the different nickel acetate concentration of table 1
| Nickel acetate concentration/mg L-1 | 5 | 15 | 25 | 35 | 45 | 55 |
| Ecorr/ V | -0.6572 | -0.5949 | -0.5344 | -0.5243 | -0.5445 | -0.6033 |
Comprehensive any of the above performance, all can obtain preferable coating, wherein preferably 25-35g/L when nickel acetate content is 5-55g/L,
Most preferably 25g/L.
Embodiment 2
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: cement base piezoelectric composite material matrix reduction treatment to be plated:
Cement base piezoelectric composite material after roughening is put in reducing solution, at room temperature soaks 10min.
Step 4: cement base piezoelectric composite material matrix activation processing to be plated:
Being taken out by cement base piezoelectric composite material after reduction immerses in activating solution, soaks 10min, make nickel ion energy at 35 DEG C
It is reduced to elemental nickel adsorb at matrix surface, and rinses well with water.Activating solution is the aqueous solution of nickel acetate, containing of nickel acetate
Amount is 25 g/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 borohydride
It is 1:1 that content is the volume ratio of 65 g/L, methanol or ethanol and water.
The scanning electron microscope (SEM) photograph of the coating that employing methanol aqueous solution obtains is shown in Fig. 2, and coating surface light, coating is smooth, crystal grain
Between combine densification, adhesion is good.Repeatedly pasting coating surface with 3M adhesive tape, result coating surface the most substantially breaks
Damage, illustrate that the adhesion of coating is excellent.With energy depressive spectroscopy, coating being carried out component analysis, cement matrix part phosphorus content reaches
6.03wt%, ceramic matrix part phosphorus content reaches 6.76wt%, and deposit in acidic electroless Ni electrolyte is higher, has preferable corrosion resistance.
The scanning electron microscope (SEM) photograph of the coating that employing ethanol water obtains is shown in Fig. 3, and coating surface light, coating is smooth, crystal grain
Between combine densification, adhesion is good.Repeatedly pasting coating surface with 3M adhesive tape, result coating surface the most substantially breaks
Damage, illustrate that the adhesion of coating is excellent.With energy depressive spectroscopy, coating being carried out component analysis, cement matrix part phosphorus content reaches
4.93wt%, ceramic matrix part phosphorus content reaches 4.39wt%.
By Fig. 2 with Fig. 3 it can be seen that the microscopic appearance of coating using different reduction solvent to obtain is different, employing
The coating surface structure cell that methanol aqueous solution obtains is less, and cement matrix is inconspicuous with the coating demarcation line on ceramic matrix, uses
The coating surface structure cell that ethanol water obtains is relatively big, and cement matrix is the most obvious with the coating demarcation line on ceramic matrix
Some.
In sum, sodium borohydride is made solvent with methanol-water mixed liquor or ethanol water mixed liquid and all can preferably be plated
Layer, uses methanol-water mixed liquor gained deposit in acidic electroless Ni electrolyte higher, and corrosion resistance is preferable, but uses the toxicity of ethanol water mixed liquid more
Low, more environmentally friendly.
Embodiment 3
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, 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:
Being taken out by cement base piezoelectric composite material after reduction immerses in activating solution, soaks 10min, make nickel ion energy at 35 DEG C
It is reduced to elemental nickel absorption rinse well with water after matrix surface, activation.
Step 5: with embodiment 1.
In above-mentioned steps 4, activating solution be the content of the aqueous solution of nickel acetate or nickel sulfate, nickel acetate or nickel sulfate be 25
g/L。
The equal surface-brightening of coating that nickel acetate and nickel sulfate obtain, smooth, intercrystalline combines densification.With 3M adhesive tape to coating
Surface is pasted repeatedly, and coating surface all less than the most damaged, illustrates that the adhesion of coating is excellent.Nickel acetate and nickel sulfate institute
The Tafel curve obtaining coating is shown in Fig. 4, from fig. 4, it can be seen that nickel sulfate activation gained corrosion resistance of coating outline is inferior to nickel acetate
Activation gained corrosion resistance of coating, therefore preferred nickel acetate.
Embodiment 4
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, and step is as follows:
Step 1: cement base piezoelectric composite material surface to be plated polishing and oil removing:
Cement base piezoelectric composite material 600#, 1000# sand paper to be plated is polished successively, more finely polishes with abrasive paper for metallograph, super
After sound cleans 10min, it is dipped in the degreasing fluid containing acetone ultrasonic cleaning 20min.
Step 2: cement base piezoelectric composite material surface coarsening to be plated processes:
Cement base piezoelectric composite material after oil removing is placed in coarsening solution roughening, processes 30min at 30 DEG C, then rinse with water dry
Only, to remove coarsening solution.The compound method of coarsening solution is: with the mass ratio of 5:1, sodium hydroxide is made into quality with sodium carbonate and divides
Number is the solution (sodium carbonate and sodium hydroxide total concentration are 35%) of 35wt%, then adds potassium permanganate and second two in this solution
Amine, potassium permanganate concentration is 5g/L, and ethylenediamine concentration is 30mL/L.
Step 3: cement base piezoelectric composite material reduction treatment to be plated:
Cement base piezoelectric composite material after roughening is put in reducing solution, at room temperature soaks 10min.Reducing solution is:
Sodium borohydride, the mixed liquor of first alcohol and water, wherein the content of sodium borohydride is 75g/L, and the volume ratio of first alcohol and water is 1:1.
Step 4: cement base piezoelectric composite material activation processing to be plated:
Will reduction after cement base piezoelectric composite material take out be directly immersed in activating solution, at 35 DEG C soak 10min, make nickel from
Son can be reduced to elemental nickel absorption and rinse well with water after matrix surface, activation.Activating solution is the aqueous solution of nickel acetate, second
The content of acid nickel is 25 g/L.
Step 5: with embodiment 1.
Gained coating naked eyes see surface-brightening, and solderability is good, and coating surface is the most smooth, fine and close, piezoelectric ceramics base and water
Without demarcation line and crack between mud base, repeatedly pasting electrode surface with 3M adhesive tape, after stickup, coating is the most complete, without bright
Showing damaged and come off, coating is well combined with base material.With energy depressive spectroscopy, coating carried out component analysis, cement matrix part phosphorus
Content reaches 5.01wt%, and ceramic matrix part phosphorus content reaches 5.59wt%.
Embodiment 5
According to the method for embodiment 4 in cement base piezoelectric composite material matrix surface nickel plating, except for the difference that: activation temperature is 25 DEG C
With 40 DEG C.
The equal surface-brightening of gained coating under 25 DEG C and 40 DEG C of activation temperatures, smooth, intercrystalline combines densification.With 3M adhesive tape pair
Coating surface is pasted repeatedly, and coating surface all less than the most damaged, illustrates that the adhesion of coating is excellent.Use energy depressive spectroscopy
Coating carries out component analysis, and at 25 DEG C, the cement matrix part phosphorus content of gained coating reaches 4.35wt%, ceramic matrix part
Phosphorus content reaches 4.87wt%.At 40 DEG C, the cement matrix part phosphorus content of gained coating reaches 4.98wt%, ceramic matrix part
Phosphorus content reaches 5.64wt%.
Embodiment 6
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, 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:
Nickel sulfate 18g/L, trisodium citrate 8g/L, sodium hypophosphite 26g/L, sodium acetate 8 g/L, Borax 6g/L, adjust with ammonia
PH is 6.5-7.5, plating temperature 45 DEG C.
Gained coating surface light, solderability is good, and coating surface is the most smooth, fine and close, with 3M adhesive tape repeatedly to coating table
Face is pasted, and after stickup, coating is the most complete, and nothing is the most damaged and comes off, and coating is well combined with base material.Divide by power spectrum
Analyzer carries out component analysis to coating, and cement matrix part phosphorus content reaches 4.84wt%, and ceramic matrix part phosphorus content reaches
5.31wt%。
Comparative example 1
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: cement base piezoelectric composite material sensitized treatment to be plated:
Cement base piezoelectric composite material after roughening is put in sensitized solution, at room temperature soaks 7min.Sensitizing solution formula: chlorine
Change stannous: 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 in activated solution, under room temperature, soaks 8min, activating solution formula: chlorination
Palladium: 0.4 g/L, 37% concentrated hydrochloric acid: 9.9mL/L.
Step 5: with embodiment 1.
Acidity is used to have palladium activation method gained coating surface dark, not exclusively, open defect seen from naked eyes, and plating speed is relatively
Little, Fig. 5 is gained coating surface scanning electron microscope and energy spectrogram, scanning figure can be seen that coating surface is uneven, have bigger
Crystal grain is reunited, and by energy spectrogram it can be seen that contain the impurity such as Si, C, O in coating, and phosphorus content is relatively low, only 1.54wt%, this
Being likely due to cement matrix suffered in acid condition to corrode, there occurs reaction with acid, therefore using has palladium activation method institute
Obtain coating performance poor.
Fig. 6 is to have palladium activation and the Tafel curve comparison diagram of no-palladium activating gained coating, as seen from the figure, uses and lives without palladium
The corrosion potential of change method gained coating significantly greater than has the corrosion potential of palladium activation method gained coating, and no-palladium activating method is described
It is more suitable for cement base piezoelectric composite material chemical nickel plating on surface.
Comparative example 2
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, and step is as follows:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: cement base piezoelectric composite material reduction treatment to be plated:
Putting in reducing solution by the cement base piezoelectric composite material after roughening, at room temperature soak 10min, reducing solution is boron
The pure methanol solution of sodium hydride, the content of sodium borohydride is 70 g/L.
Step 4: with embodiment 1.
Step 5: with embodiment 1.
Using pure methanol to be prone to volatilization as sodium borohydride solvent, be difficult to operation, gained coating is poor with basal body binding force,
It is relatively big that this is probably sodium borohydride activity in pure methanol, forms more active centre at matrix surface and makes that plating speed is excessive to be made
Becoming, in terms of naked eyes, coating surface is uneven, and cement matrix and ceramic matrix exist crack, and Fig. 7 is coating surface morphology figure,
By in figure it can also be seen that coating surface is uneven, have bigger crystal grain to reunite, the crack in cement matrix and ceramic matrix is relatively big,
Do not covered by coating, therefore use pure methanol to make sodium borohydride solvent and can not obtain coating of good performance.
Comparative example 3
To above-mentioned 8 × 8mm2, thickness is that the cement base piezoelectric composite material surface of 2mm carries out nickel plating, 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:
Nickel sulfate 30g/L, trisodium citrate 20g/L, sodium hypophosphite 20g/L, sodium acetate 12 g/L, Borax 8g/L, adjust with ammonia
Whole pH is 6.5-7.5, and plating temperature is 45 DEG C.
As shown in Figure 8, as seen from the figure, coating surface is uneven, out-of-flatness for gained coating surface morphology, and cement matrix and
There is bigger crystal grain and pile up and reunite in ceramic matrix intersection.Additionally, the adhesion of coating is the most poor, with 3M adhesive tape repeatedly to plating
Layer surface is pasted, and after stickup, coating surface has breakage and obscission.Therefore the selection of nickel-plating liquid is for the performance of coating
There is considerable influence.
Cannot be exhaustive for embodiments of the present invention, example above is only to be arranged some embodiments of the present invention
Lift and explanation, on the basis of above example, change piezoelectric ceramics, epoxy resin and the kind of cement, change Piezoelectric anisotropy
The type of material also can obtain effective coating.
Claims (10)
1. a preparation method for cement base piezoelectric composite material surface nickel electrode, including to cement base piezoelectric composite material surface
Carry out being roughened, reduce, activate, the step of Nickel Plating Treatment, it is characterized in that: be roughened and carry out, used by reduction in alkalescence coarsening solution
Reducing solution is methanol aqueous solution or the ethanol water of sodium borohydride of sodium borohydride, and the activating solution used by activation is nickel acetate
Aqueous solution or nickel sulfate solution, the nickel-plating liquid used by nickel plating consists of: nickel sulfate 18-22g/L, trisodium citrate 8-16g/L,
Sodium hypophosphite 26-32g/L, sodium acetate 8-14 g/L, Borax 6-10g/L, pH are 6.5-7.5.
Preparation method the most according to claim 1, is characterized in that: described cement base piezoelectric composite material refers to make pottery with piezoelectricity
Porcelain is functive, the piezo-electricity composite material formed for matrix with the mixture of epoxy resin and cement.
Preparation method the most according to claim 1 and 2, is characterized in that: the compound method of coarsening solution is: by sodium hydroxide with
Sodium carbonate mixes with the mass ratio of 5:1, is made into sodium carbonate and sodium hydroxide total mass fraction is the aqueous solution of 35wt%, then to
Adding potassium permanganate and ethylenediamine in this solution, to make potassium permanganate concentration be 5g/L, ethylenediamine concentration is 30mL/L, obtains roughening
Liquid.
Preparation method the most according to claim 1 and 2, is characterized in that: in reducing solution, and the content of sodium borohydride is 65-
75 g/L。
5. according to the preparation method described in claim 1 or 4, it is characterized in that: in reducing solution, methanol or ethanol and the volume of water
Ratio is 1:1.
Preparation method the most according to claim 1, is characterized in that: in activating solution, and the content of nickel acetate or nickel sulfate is 5-
55 g/L, preferably 25-35g/L, most preferably 25g/L.
Preparation method the most according to claim 1, is characterized in that: roughening is carried out at 30 DEG C；Reduction is at room temperature carried out；
Activation is carried out at 25 DEG C-40 DEG C；Nickel plating is carried out at 45-50 DEG C.
Preparation method the most according to claim 6, is characterized in that: activation is carried out at 35 DEG C, and nickel plating is carried out at 45 DEG C.
9. according to the preparation method described in claim 1,7 or 8, it is characterized in that: coarsening time is 30min, reduce and activate
Time is 10min.
Preparation method the most according to claim 1, is characterized in that, comprises the following steps:
(1) carry out polishing and oil removing by cement base piezoelectric composite material surface；
(2) being placed in coarsening solution by the cement base piezoelectric composite material after oil removing and carry out roughening treatment, after process, water rinses；
(3) cement base piezoelectric composite material after being roughened is put into and is carried out reduction treatment in reducing solution, the cement based after reduction
Piezo-electricity composite material places into and carries out activation processing in activating solution；
(4) after activation, being taken out by cement base piezoelectric composite material, water rinses, and adds in nickel-plating liquid and carries out chemical nickel plating, and coating reaches
To stopping nickel plating during desired thickness, obtain nickel coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111763931A (en) * | 2020-07-15 | 2020-10-13 | 上海大学 | Preparation method of nickel-plated glass microspheres and product |
| CN112831776A (en) * | 2021-02-08 | 2021-05-25 | 福州大学 | Method for metalizing 3-3 type ceramic-polymer dielectric composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2760028Y (en) * | 2004-07-26 | 2006-02-22 | 济南大学 | Cement-based piezoelectric composite material |
| CN102337526A (en) * | 2011-09-15 | 2012-02-01 | 济南大学 | Preparation method of nickel electrode made of piezoelectric composite material |
| CN102924020A (en) * | 2012-10-26 | 2013-02-13 | 青岛理工大学 | Piezoresistance/piezoelectric composite material, manufacturing method of material, sensor utilizing material and manufacturing method of sensor |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2760028Y (en) * | 2004-07-26 | 2006-02-22 | 济南大学 | Cement-based piezoelectric composite material |
| CN102337526A (en) * | 2011-09-15 | 2012-02-01 | 济南大学 | Preparation method of nickel electrode made of piezoelectric composite material |
| CN102924020A (en) * | 2012-10-26 | 2013-02-13 | 青岛理工大学 | Piezoresistance/piezoelectric composite material, manufacturing method of material, sensor utilizing material and manufacturing method of sensor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763931A (en) * | 2020-07-15 | 2020-10-13 | 上海大学 | Preparation method of nickel-plated glass microspheres and product |
| CN112831776A (en) * | 2021-02-08 | 2021-05-25 | 福州大学 | Method for metalizing 3-3 type ceramic-polymer dielectric composite material |
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