CN105586581B - A kind of method in cement base piezoelectric composite material chemical nickel plating on surface - Google Patents
A kind of method in cement base piezoelectric composite material chemical nickel plating on surface Download PDFInfo
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- CN105586581B CN105586581B CN201610124942.XA CN201610124942A CN105586581B CN 105586581 B CN105586581 B CN 105586581B CN 201610124942 A CN201610124942 A CN 201610124942A CN 105586581 B CN105586581 B CN 105586581B
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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
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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
- C23C18/18—Pretreatment of the material to be coated
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Abstract
The invention discloses a kind of method in cement base piezoelectric composite material chemical nickel plating on surface, including being roughened, reducing, activating, nickel plating the step of, roughening is carried out in alkaline coarsening solution, reducing solution used is the methanol or ethanol water of sodium borohydride, activating solution used is the aqueous solution of the nickel acetate containing additive or nickel sulfate, and nickel-plating liquid is：The 22g/L of nickel sulfate 18, the 16g/L of trisodium citrate 8, the 32g/L of sodium hypophosphite 26, the g/L of sodium acetate 8 14, borax 6 10g/L, pH are 6.5 7.5.The present invention is suitable for the various cement base piezoelectric composite materials using piezoelectric ceramics as functive, using cement and epoxy resin as matrix, cost is relatively low, the feature of environmental protection is more preferable, gained coating surface is smooth, uniformity, and corrosion resistance is good, good conductivity, solderability are strong, it is tightly combined with cement base piezoelectric composite material, difficult for drop-off, adhesion is good, has good application prospect.
Description
Technical field
The present invention relates to a kind of method in cement base piezoelectric composite material plating nickel on surface, and in particular to one kind is in cement base
Method of the piezo-electricity composite material surface without palladium salt activating chemical nickel plating, belongs to Chemical Plating of Non metal Material technical field.
Background technology
Piezoelectric is widely used in the health monitoring of large scale civil engineering because of its special data-collection characteristic.
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 typically relatively low.And their toughness are poor, fragility cracking, cause
Device reliability by its making is not high, poor durability.Piezo-electricity composite material is to start the 1980s to rise the new of research
Type piezoelectric, it is the shape using piezoelectric ceramics as functive using polymer such as epoxy resin, rubber or PVDF as matrix
Into composite.It combines the characteristics of piezoelectric ceramics and polymer, has the spies such as dielectric constant small, density is low, good toughness
Point, but polymer matrix piezo-electricity composite material still suffers from some defects, such as polarizing, difficult, piezoelectric property is not high, can not be fine
The health monitoring 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 with concrete compatibility is good, intensity is high, good endurance, perceive it is sensitive
The features such as degree height and low cost, its development are transforming conventional cement sill, expand its application field and are promoting all kinds of buildings
Engineering structure has an extensive engineer applied meaning to intelligent direction development, thus in field of civil engineering more and more by
The attention of people.But because the cement base piezoelectric composite material is by three kinds of cement, polymer, piezoelectric ceramics different materials
What material was combined with each other, cement is binder materials, and polymer is high molecular polymer, piezoelectric ceramics is typical inorganic non-metallic
Material, the components of three kinds of materials, technical process, Forming Mechanism and mechanical property, surface state and other materials after being formed
Characteristic is all different, if making metal coating have good adhesive strength on these three materials simultaneously and reaching uniformity
Property is extremely difficult, so as to limit the use 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, cement base piezoelectric composite material is set to play excellent piezoelectric property, to water
The popularization and application of mud base piezoelectric composite material have very important significance.
Chemical nickel plating turns into nonmetallic materials because its coating has good hardness, corrosion resistance, electric conductivity and solderability etc.
The effective means of surface metalation.Traditional chemical plating of non-metal material nickel technique uses PdCl2Carry out acid roughening-acidity
Sensitization-acidic activated-nickel plating technology, the process treatment process is more complicated, PdCl2It is expensive and there is toxicity, grain is urged
It is strong to change activity, has palladium particle to fall into plating solution unavoidably in plating process, influences the stability of plating solution.In addition, palladium salt is lived
Change method need to be carried out in acid condition, and acid has very strong corrosive effect, therefore palladium salt activation method nickel plating discomfort Heshui to cement
Mud base piezoelectric composite material.
At present cement base piezoelectric composite material surface carry out the method without palladium salt activating chemical nickel plating there is no literature reported on,
Therefore research and develop a kind of suitable cement base piezoelectric composite material, be roughened, be sensitized, activated in alkalescence or neutral medium
To avoid the nickel chemical plating technology of erosion of the acid medium to cement base piezoelectric composite material, for cement base piezoelectric composite material
Application and development and nickel chemical plating technology process improvement it is significant.In addition, use saving noble metal, reduce work
Skill cost is also significant.
The content of the invention
It is an object of the invention to provide a kind of method in cement base piezoelectric composite material chemical nickel plating on surface, this method root
The characteristics of according to cement base piezoelectric composite material, chemical nickel plating method and technological parameter are improved and optimized, the nickel of gained
Quality of coating is good, is combined with cement base piezoelectric composite material.
Before this, inventor has successfully worked out polymer matrix piezo-electricity composite material plating nickel on surface technique, and declares
Patent, Application No.：201110271920.3.But because the self character of cement and polymer has very big difference,
Experiment proves that this method is appropriate only for the composite of polymer and piezoelectric ceramics composition, it is not appropriate for cement base piezoelectric and answers
Condensation material.Also, this method is required in roughening, sensitization, activation process using acid, and this has very big corrosion to make to cement
With being less suitable for cement base piezoelectric composite material.Therefore, inventor is directed to cement base piezoelectric composite material self-characteristic, leads to
Cross numerous studies and experiment has obtained the chemical nickel plating method of suitable cement base piezoelectric composite material, technological process is：Roughening-also
Original-activation-nickel plating, whole process are all implemented under neutral or basic conditions, both effectively prevent acid condition to cement base pressure
The erosion of composite, coating of good performance can be obtained on cement base piezoelectric composite material surface again.
Cement base piezoelectric composite material described in the present invention, refer to using piezoelectric ceramics as functive, with polymer and water
The mixture of mud is the piezo-electricity composite material that matrix is formed.The piezoelectric ceramics can be various disclosed piezoelectric ceramics, such as
PMN-ZT, PZT piezoelectric ceramics；The cement can be in the prior art it is disclosed, piezo-electricity composite material matrix can be used as
Various cement, such as Portland cement；The polymer can be disclosed in the prior art, can make with cement mixing
For the various polymer of matrix, Inventive polymers refer in particular to epoxy resin.Cement base piezoelectric composite material of the present invention can be with
It is the types such as 1-3 types, 0-3 types, 1-1 types.In preparation process, in order that piezo-electricity composite material shaping is good, except piezoelectricity is made pottery
Outside porcelain, cement and polymer, the auxiliary agent of some assistant formations, such as curing agent, diluent etc. also inevitably be present.When
During its plating nickel on surface, nickel needs simultaneously and piezoelectric ceramics, cement, polymer three form strong bonded, the nickel electricity so obtained
Pole could be well combined with cement base piezoelectric composite material, considerably increase the difficulty of nickel plating.
Present invention research has obtained the method for being adapted to above-mentioned cement base piezoelectric composite material chemical nickel plating on surface, this method bag
Include cement base piezoelectric composite material surface is roughened, reduced, is activated, Nickel Plating Treatment the step of, wherein, be roughened in alkaline coarse
Change and carried out in liquid, reduce reducing solution used as the methanol aqueous solution of sodium borohydride or the ethanol water of sodium borohydride, it is living
Change activating solution used as the nickel acetate containing additive or the aqueous solution of nickel sulfate, the nickel-plating liquid composition used in nickel plating is：Sulphur
Sour nickel 18-22g/L, trisodium citrate 8-16g/L, sodium hypophosphite 26-32g/L, sodium acetate 8-14 g/L, borax 6-10g/L,
PH is 6.5-7.5.
Further, in the inventive method, it is additionally included in before roughening and surface is carried out to cement base piezoelectric composite material surface
The step of polishing, oil removing.
Further, in the inventive method, it is the aqueous solution to be roughened coarsening solution used, and the compound method of coarsening solution is：Will
Sodium hydroxide is with sodium carbonate with 5:1 mass ratio mixing, it is the water-soluble of 35wt% to be made into sodium carbonate and sodium hydroxide total mass fraction
Liquid, potassium permanganate and ethylenediamine are then added into the solution, makes potassium permanganate concentration be 5g/L, ethylenediamine concentration is 30mL/
L, produce coarsening solution.
Further, it is roughened in 30 DEG C or so lower progress.It is 30min or so the time required to general roughening.
Further, reducing solution of the present invention be sodium borohydride methanol aqueous solution or ethanol water, activating solution into
It is divided into nickel acetate or nickel sulfate, additive and water, the additive is KI, lauryl sodium sulfate, ethylenediamine or poly- second
Glycol.The present invention has produced active nickel using the collocation of sodium borohydride and nickel salt with sodium borohydride reduction（Activate a little）, the party
The activation point that method obtains can be uniformly distributed on cement base piezoelectric composite material surface, nickel dam in follow-up Ni-Speed is existed
It is uniformly distributed on piezoelectric ceramics, cement and polymer, phenomena such as will not causing to be layered, come off, for being smoothed out for follow-up nickel plating
Provide 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 overcomes
Palladium salt activation must use the deficiency that acid adversely affects to cement.In reduction process, sodium borohydride is in reducing solution
Effect is preferable when content is 65-75 g/L.In activation process, the content of nickel acetate or nickel sulfate in activating solution is 5-55 g/L
Shi Xiaoguo is preferable, by experimental verification, when nickel salt concentration is 25-35g/L in activating solution, and nickel plating speed and corrosion resistance of coating
Preferably, therefore the preferably concentration of nickel salt is 25-35g/L, most preferable concentrations 25g/L.
In the present invention, reducing solution selection methanol aqueous solution or ethanol water are solvent, and activating solution selection water is solvent.
The selection of solvent has considerable influence for the uniformity of activation point, the firmness of activation point, to the uniformity and cement base of nickel dam
Piezo-electricity composite material combined with firmness also have a major impact.Characteristic of the invention according to cement base piezoelectric composite material, through excessive
Amount experimental study has obtained required solvent, and when sodium borohydride is dissolved in alcohol solution, gained quality of coating is good.It is preferred that
, when the volume ratio of methanol or ethanol and water is 1:When 1, effect is best.
In the inventive method, sodium borohydride reduction, nickel salt activation are selected, reduction can carry out at room temperature, and activation can be with
Carried out at 25 DEG C -40 DEG C, it is preferably relatively low in 35 DEG C or so lower progress, temperature.Reduction and activation are within a short period of time
It can complete, in general, in 10min or so the time required to reduction and activation.
Further, in activating solution, the content of additive is 20-30mg/L, and the additive is KI, dodecane
Base sodium sulphate, ethylenediamine or polyethylene glycol, preferably polyethylene glycol.It is demonstrated experimentally that the addition of additive can make activation point minute
Cloth is more uniformly distributed, and makes coating and cement base piezoelectric composite material associativity more preferable, is advantageous to improve plating speed, the plated crystal of formation
Grow, metallic luster is good, and surface topography more preferably, can also improve the corrosion resistance of coating.In addition, after adding additive, it is living
It is more firm on cement base piezoelectric composite material surface to change point absorption, is not easy to come off in Ni-Speed, nickel-plating liquid will not be made
Into pollution, so that nickel-plating liquid can be used repeatedly, the stability and service life of nickel-plating liquid are improved, reduces nickel plating
The number of liquid post processing, reduces pollution of the nickel-plating liquid to environment, has been greatly reduced cost.Further, after adding additive, plating
The phosphorus content of layer has been lifted, and according to the literature, phosphorus content is relevant with coating corrosion resistance, and phosphorus content is higher, and coating is corrosion-resistant
Property is better.It can thus be seen that the addition of additive also increases the corrosion resistance of coating.
After activated processing forms activation point, cement base piezoelectric composite material can carry out Nickel Plating Treatment.Used in the present invention
Nickel-plating liquid be nickel sulfate the aqueous solution, nickel-plating liquid both needed to arrange in pairs or groups each other with reducing solution and activating solution, and needed to meet water again
The characteristic of mud base piezoelectric composite material in itself, inventor pass through numerous studies, have obtained suitable nickel-plating liquid of the invention, wherein,
Best results during nickel-plating liquid selection following content：Nickel sulfate 20g/L, trisodium citrate 12g/L, sodium hypophosphite 30g/L,
The g/L of sodium acetate 12, borax 8g/L, pH 6.5-7.5.Nickel-plating liquid pH weakly acidic pHs of the present invention, stability is good, is not easily decomposed, can
Resting period is grown, and the nickel-plating liquid of weakly acidic pH overcomes nickel-plating liquid slant acidity to cause burn into cement base piezoelectric composite material
The deficiencies of nickel dam quality reduces obtained by nickel-plating liquid meta-alkalescence, plating solution is unstable.In addition, pass through the cooperation of each component, gained
Coating can reach uniformity, it is corrosion-resistant, adhesion is good the advantages that.
Further, nickel-plating liquid can adjust pH with ammoniacal liquor.
Further, nickel plating is in 45 DEG C or so progress, such as 45-50 DEG C.Plating time is relevant with the thickness of gained nickel dam,
When plating time is 15-20min or so, nickel layer thickness can reach 2 μm or so, adjustment time can be closed as needed
Suitable thickness.According to the report of prior art, it is necessary at a higher temperature in the nickel-plating liquid of partial neutral, such as 60-70 DEG C
Nickel plating could be preferably carried out, and nickel plating temperature of the present invention only needs 45 DEG C or so, reduces energy consumption and as caused by high temperature
Plating solution unstable the defects of waiting, this with handling well early stage of the invention, the activation point of formation is evenly distributed, be distributed more have compared with high point
System.Under the conditions of this nickel plating, the plated layer compact of gained, uniform, adhesion is good, good quality.
The method of nickel plating of the present invention, specifically includes following steps：
（1）Cement base piezoelectric composite material surface is polished and oil removing；
（2）Cement base piezoelectric composite material after oil removing is placed in coarsening solution and carries out roughening treatment, water rinses after processing；
（3）Cement base piezoelectric composite material after roughening is put into reducing solution and carries out reduction treatment, the water after reduction
Mud base piezoelectric composite material, which places into, carries out activation process in activating solution；
（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, plates
Layer stops nickel plating when reaching required thickness, produces nickel coating.
The present invention is directed to the acid nonfast particularity of cement base piezoelectric composite material, there is provided in cement base piezoelectric composite material
The chemical nickel plating method that surface activates without palladium salt, it is pre- that this method first passes through mechanical grinding early stage, oil removing, roughening, reduction, activation etc.
Processing makes its surface form autocatalytic activity center, then carries out chemical nickel plating again, and the whole no acidic reagent of Ni-Speed is intervened,
Cement base piezoelectric composite material will not be caused to damage.The present invention has advantages below：
1st, the present invention produces active nickel using sodium borohydride reduction at normal temperatures, and activating substitution palladium salt with nickel activates, science,
Rationally, cost is relatively low, and the feature of environmental protection is more preferable.
2nd, nickel-plating liquid weakly acidic pH of the present invention, stability is good, is not easily decomposed, and can grow the resting period.
3rd, nickel plating process of the present invention be suitable for it is various using piezoelectric ceramics as functive, using cement and epoxy resin as matrix
Cement base piezoelectric composite material.Nickel plating is carried out under cryogenic, and energy consumption is low, and repetitive rate is high, by the cooperation of each process conditions,
Metal nickel dam can be plated simultaneously on piezoelectric ceramics and cement matrix, be provided for the subsequent applications of cement base piezoelectric composite material
Facility.
4th, 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
Cause, corrosion resistance is good, good conductivity, solderability are strong, is tightly combined with cement base piezoelectric composite material, difficult for drop-off, adhesion is good
It is good, there is good application prospect.
Brief description of the drawings
Influence of Fig. 1 acetic acid nickel concentration to plating speed.
Fig. 2 methanol-waters make the SEM figures of coating obtained by solvent（3000 times）.
Fig. 3 alcohol-waters make the SEM figures of coating obtained by solvent（3000 times）.
The Tafel curve of Fig. 4 nickel acetates and nickel sulfate activation gained coating.
The SEM figures of gained coating when Fig. 5 additives are KI（3000 times）.
The SEM figures of gained coating when Fig. 6 additives are lauryl sodium sulfate（3000 times）.
The SEM figures of gained coating when Fig. 7 additives are ethylenediamine（3000 times）.
The SEM figures of gained coating when Fig. 8 additives are polyethylene glycol（3000 times）.
The SEM figures of gained coating when Fig. 9 additives are cetyl trimethylammonium bromide（3000 times）.
Influence of Figure 10 different additives to deposit in acidic electroless Ni electrolyte.
Figure 11 has coating surface SEM+EDS figures obtained by palladium activation method.
Figure 12 has palladium activation and coating Tafel curve obtained by no-palladium activating.
The SEM figures of the gained coating of Figure 13 comparative examples 2（3000 times）.
The SEM figures of the gained coating of Figure 14 comparative examples 3（3000 times）.
Embodiment
Below by specific embodiment, the present invention will be further elaborated, and the description below is merely to explain this hair
It is bright, its content is not defined.
In the inventive method, the corrosion resistance of coating is determined using electrochemical workstation, specific method is with 3.5% chlorine
Change sodium solution is etchant solution, and using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, and corroded area is
1.5cm2, the V/s of sweep speed 0.1, the s of stand-by period 2.
In the inventive method, the plating speed of coating is determined using weight method：
In formula：vFor plating speed（g·dm-2·h-1）；ΔmFor the weightening of plating piece before and after plating（g）；SFor plate areas（dm2）；tFor plating time（ h）.
In the inventive method, morphology analysis is carried out to nickel coating using ESEM.
In the inventive method, constituent analysis is carried out to coating using energy depressive spectroscopy.
In following embodiments, by taking 1-3 type cement base piezoelectric composite materials as an example, Ni-Speed and each technique ginseng is discussed in detail
Influence of the number change to nickel plating effect.Cement base piezoelectric composite material used is using PZT-5 piezoelectric ceramics as functive, with ordinary silicon
The mixture of acid salt cement, epoxy resin and curing agent is prepared, epoxy resin can as matrix using cutting-casting
To be the various epoxy resin that can be used for piezo-electricity composite material, such as glycidol amine or linear aliphatic class asphalt mixtures modified by epoxy resin
Fat, such as AB- grouting resins.Preparation method is：The direction that cutting machine is polarized along piezoelectric ceramics, the body according to shared by ceramic phase
Fraction, the piezoelectric ceramics post of required size is accurately cut out successively；Using supersonic wave cleaning machine to the piezoelectric ceramics after cutting
Block is cleaned by ultrasonic, and to remove residual debris therein, is then dried the piezoelectric ceramics block after cleaning and is placed in mould；
By cement, epoxy resin and curing agent 4：4：1 mass ratio prepares matrix material, and vacuumize process is carried out after being sufficiently stirred, and
Matrix after processing is cast in mould, and carries out vacuumize process again；Sample is cut and polishing, until
The surface of sample two is completely exposed piezoelectric ceramics post；Finally prepare cement base piezoelectric composite material.Gained cement base piezoelectric is compound
The size of material is 8 × 8mm2, thickness 2mm.
Embodiment 1
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 2mm carries out nickel plating, and step is as follows：
Step 1：The polishing of cement base piezoelectric composite material surface and oil removing to be plated：
Cement base piezoelectric composite material to be plated is polished successively with 600#, 1000# sand paper, then finely thrown with abrasive paper for metallograph
Light, after being cleaned by ultrasonic 10min, it is dipped in the degreasing fluid containing acetone and is cleaned by ultrasonic 20min.
Step 2：Cement base piezoelectric composite material surface coarsening processing to be plated：
Cement base piezoelectric composite material after oil removing is placed in coarsening solution and is roughened, 30min is handled at 30 DEG C, then rushed with water
Wash clean, to remove coarsening solution.The compound method of coarsening solution is：By sodium hydroxide and sodium carbonate with 5:1 mass ratio is made into matter
Measure the solution that fraction is 35wt%（Sodium carbonate and sodium hydroxide total concentration are 35%）, then into the solution add potassium permanganate and
Ethylenediamine, potassium permanganate concentration are 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 into reducing solution, soaks 10min at room temperature.Reducing solution
For：The content of the mixed liquor of sodium borohydride, first alcohol and water, wherein 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 process to be plated：
Cement base piezoelectric composite material after reduction is taken out and is directly immersed in activating solution, 10min is soaked at 35 DEG C, makes
Nickel ion can be reduced to elemental nickel absorption and be rinsed well after matrix surface, activation with water.
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
For：Nickel sulfate 20g/L, trisodium citrate 12g/L, sodium hypophosphite 30g/L, the g/L of sodium acetate 12, borax 8g/L, use ammonia
Water 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 multiple 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, shadow of the test acetic acid nickel content to coating
Ring.
The performance of the coating to being obtained under different activation solution concentrations is tested respectively.Gained coating naked eyes under each concentration
Equal shiny appearance is seen, solderability is good, and coating surface is more smooth, fine and close, and repeatedly electrode surface is glued with 3M adhesive tapes
Patch, coating is very complete after stickup, without obvious damaged and come off, each coating combined with piezo-electricity composite material surface it is good,
Macroscopically the line of demarcation between cement matrix and ceramic matrix is not seen in each coating surface.
Fig. 1 is shown in influence of the acetic acid nickel concentration to plating speed, it can be seen that nickel plating speed is dense with main salt nickel acetate is activated
The rise of degree and increase, when in the range of 5-25 g/L, it is more obvious to plate fast amplification, almost linear to increase, in 25-55 g/L
In the range of when, although plating speed with the rise of acetic acid nickel concentration also has increase, amplification slows down.
Acetic acid nickel concentration is had a certain impact to corrosion resistance coating, and the self-corrosion of coating is obtained under different acetic acid nickel concentrations
Current potential is as shown in table 1, and more just, corrosion resistance of coating is better, as can be seen from Table 1 for corrosion potential：With acetic acid nickel concentration
Increase, corrosion potential are shuffled, and when acetic acid nickel concentration is 25-35g/L, this scope shuffles maximum, and corrosion resistance is best, exceeds
This scope, shuffling has reduction, and corrosion resistance is deteriorated.
The corrosion potential of coating is obtained under the different acetic acid nickel concentrations of table 1
| Acetic acid nickel concentration/mgL-1 | 5 | 15 | 25 | 35 | 45 | 55 |
| E corr/ V | -0.6572 | -0.5949 | -0.5344 | -0.5243 | -0.5445 | -0.6033 |
In summary various performances, acetic acid nickel content can obtain preferable coating when being 5-55g/L, wherein it is preferred that 25-
35g/L, most preferably 25g/L.
Embodiment 2
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 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 into reducing solution, soaks 10min at room temperature.
Step 4：Cement base piezoelectric composite material matrix activation process to be plated：
By after reduction cement base piezoelectric composite material take out immerse activating solution in, soak 10min at 35 DEG C, make nickel from
Son can be reduced to elemental nickel absorption and be rinsed well in matrix surface, and with water.Activating solution be nickel acetate the aqueous solution, nickel acetate
Content be 25 g/L.
Step 5：With embodiment 1.
In above-mentioned steps 3, reducing solution is respectively the methanol aqueous solution or ethanol water of sodium borohydride, sodium borohydride
Content is that the volume ratio of 65 g/L, methanol or ethanol and water is 1:1.
The scanning electron microscope (SEM) photograph of the coating obtained using methanol aqueous solution is shown in Fig. 2, and coating surface is bright, and coating is smooth, crystal grain
Between combine densification, adhesion is good.Coating surface is pasted repeatedly with 3M adhesive tapes, as a result coating surface is not substantially broken
Damage, illustrates that the adhesion of coating is excellent.Constituent analysis is carried out to coating with energy depressive spectroscopy, cement matrix part phosphorus content reaches
6.03wt%, ceramic matrix part phosphorus content reach 6.76wt%, and deposit in acidic electroless Ni electrolyte is higher, have preferable corrosion resistance.
The scanning electron microscope (SEM) photograph of the coating obtained using ethanol water is shown in Fig. 3, and coating surface is bright, and coating is smooth, crystal grain
Between combine densification, adhesion is good.Coating surface is pasted repeatedly with 3M adhesive tapes, as a result coating surface is not substantially broken
Damage, illustrates that the adhesion of coating is excellent.Constituent analysis is carried out to coating with energy depressive spectroscopy, cement matrix part phosphorus content reaches
4.93wt%, ceramic matrix part phosphorus content reach 4.39wt%.
The microscopic appearance of the coating obtained it can be seen from Fig. 2 and Fig. 3 using different reduction solvents is different, is used
The coating surface structure cell that methanol aqueous solution obtains is smaller, cement matrix and the coating line of demarcation unobvious on ceramic matrix, uses
The coating surface structure cell that ethanol water obtains is larger, and cement matrix and the coating line of demarcation on ceramic matrix are comparatively obvious
Some.
In summary, sodium borohydride makees solvent with methanol water mixed liquid or ethanol water mixed liquid can preferably be plated
Layer, higher using deposit in acidic electroless Ni electrolyte obtained by methanol water mixed liquid, corrosion resistance is preferable, but uses the toxicity of ethanol water mixed liquid more
It is low, it is more environmentally friendly.
Embodiment 3
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 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 process to be plated：
By after reduction cement base piezoelectric composite material take out immerse activating solution in, soak 10min at 35 DEG C, make nickel from
Son can be reduced to elemental nickel absorption and be rinsed well after matrix surface, activation with water.
Step 5：With embodiment 1.
In above-mentioned steps 4, activating solution is the aqueous solution of nickel acetate or nickel sulfate, and the content of nickel acetate or nickel sulfate is 25
g/L。
The equal surface-brightening of coating that nickel acetate and nickel sulfate obtain, smooth, intercrystalline combines fine and close.With 3M adhesive tapes to coating
Surface is pasted repeatedly, and coating surface without obvious breakage, illustrates that the adhesion of coating is excellent.Nickel acetate and nickel sulfate institute
The Tafel curve for 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, the cement base piezoelectric composite material surface that thickness is 2mm carries out nickel plating, and step is as follows：
Step 1：The polishing of cement base piezoelectric composite material surface and oil removing to be plated：
Cement base piezoelectric composite material to be plated is polished successively with 600#, 1000# sand paper, then finely thrown with abrasive paper for metallograph
Light, after being cleaned by ultrasonic 10min, it is dipped in the degreasing fluid containing acetone and is cleaned by ultrasonic 20min.
Step 2：Cement base piezoelectric composite material surface coarsening processing to be plated：
Cement base piezoelectric composite material after oil removing is placed in coarsening solution and is roughened, 30min is handled at 30 DEG C, then rushed with water
Wash clean, to remove coarsening solution.The compound method of coarsening solution is：By sodium hydroxide and sodium carbonate with 5:1 mass ratio is made into matter
Measure the solution that fraction is 35wt%（Sodium carbonate and sodium hydroxide total concentration are 35%）, then into the solution add potassium permanganate and
Ethylenediamine, potassium permanganate concentration are 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 into reducing solution, soaks 10min at room temperature.Reducing solution
For：The content of the mixed liquor of sodium borohydride, first alcohol and water, wherein 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 process to be plated：
Cement base piezoelectric composite material after reduction is taken out and is directly immersed in activating solution, 10min is soaked at 35 DEG C, makes
Nickel ion can be reduced to elemental nickel absorption and be rinsed well after matrix surface, activation with water.Activating solution is water-soluble for nickel acetate
Liquid, the content of nickel acetate is 25 g/L.
Step 5：With embodiment 1.
Gained coating naked eyes see surface-brightening, and solderability is good, and coating surface is more smooth, fine and close, piezoelectric ceramics base and water
Without line of demarcation and crack between mud base, repeatedly electrode surface is pasted with 3M adhesive tapes, coating is still very complete after stickup, without bright
Show damaged and come off, coating is well combined with base material.Constituent analysis, cement matrix part phosphorus are carried out to coating with energy depressive spectroscopy
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, the difference is that：Activation temperature is
25 DEG C and 40 DEG C.
The equal surface-brightening of gained coating under 25 DEG C and 40 DEG C of activation temperatures, smooth, intercrystalline combines fine and close.With 3M adhesive tapes pair
Coating surface is pasted repeatedly, and coating surface without obvious breakage, illustrates that the adhesion of coating is excellent.Use energy depressive spectroscopy
To coating progress constituent analysis, the cement matrix part phosphorus content of gained coating reaches 4.35wt%, ceramic matrix part at 25 DEG C
Phosphorus content reaches 4.87wt%.The cement matrix part phosphorus content of gained coating reaches 4.98wt%, ceramic matrix part at 40 DEG C
Phosphorus content reaches 5.64wt%.
Embodiment 6
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 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 activation process to be plated：
Cement base piezoelectric composite material after reduction is taken out and immersed in different activating solutions, soaks 10min at 35 DEG C,
Enable nickel ion to be reduced to elemental nickel absorption to rinse well in matrix surface, and with water.
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 iodate
Potassium, lauryl sodium sulfate, ethylenediamine, polyethylene glycol, cetyl trimethylammonium bromide.The content of nickel acetate is equal in activating solution
For 25g/L, the content of additive is 30mg/L, while does blank control with the coating obtained by additive-free activating solution.
After adding different additives, gained coating from visually seeing between cement base and piezoelectric ceramics base without obvious boundary,
Coating is integral.Fig. 5 to Fig. 9 is that KI, lauryl sodium sulfate, ethylenediamine, polyethylene glycol, 16 are added in activating solution
The SEM figures of coating during alkyl trimethyl ammonium bromide, it can be seen that adding the equal surface light of coating obtained by different additive
Bright, smooth, intercrystalline combines fine and close.Coating surface to be pasted repeatedly with 3M adhesive tapes, coating surface is no obvious damaged,
Illustrate that the adhesion of coating is excellent.
Figure 10 is that the deposit in acidic electroless Ni electrolyte contrast obtained by different additive is added in activating solution, it can be seen that adding
After KI, lauryl sodium sulfate, ethylenediamine, polyethylene glycol, deposit in acidic electroless Ni electrolyte has different degrees of raising, illustrates additive
Addition add the corrosion resistance of coating, wherein after adding polyethylene glycol, cement matrix part phosphorus content reaches 9.97wt%,
Ceramic matrix part phosphorus content reaches 10.45wt%, and synergistic effect is most obvious.And after adding cetyl trimethylammonium bromide, plating
The phosphorus content of layer reduces, and corrosion resistance reduces.It can thus be seen that addition KI, lauryl sodium sulfate, ethylenediamine, poly-
After ethylene glycol, coating intercrystalline is tightly combined, coating morphology be improved significantly, add polyethylene glycol after coating morphology improve most
Significantly, to add cetyl trimethylammonium bromide ineffective.
Embodiment 7
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 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
For：Nickel sulfate 18g/L, trisodium citrate 8g/L, sodium hypophosphite 26g/L, the g/L of sodium acetate 8, borax 6g/L, use ammoniacal liquor
Adjustment pH is 6.5-7.5,45 DEG C of plating temperature.
Gained coating surface is bright, and solderability is good, and coating surface is more smooth, fine and close, with 3M adhesive tapes repeatedly to coating table
Face is pasted, and coating is still very complete after stickup, without obvious breakage and is come off, coating is well combined with base material.With power spectrum point
Analyzer carries out constituent 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, the cement base piezoelectric composite material surface that thickness is 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 into sensitized solution, soaks 7min at room temperature.Sensitizing solution is matched somebody with somebody
Side：Stannous chloride：30g/L, 37% concentrated hydrochloric acid：50mL/L.
Step 4：Cement base piezoelectric composite material activation process to be plated：
Cement base piezoelectric composite material after sensitization is put into activated solution, soaks 8min at room temperature, activates formula of liquid：
Palladium bichloride：0.4 g/L, 37% concentrated hydrochloric acid：9.9mL/L.
Step 5：With embodiment 1.
Have that coating surface obtained by palladium activation method is dark using acidity, not exclusively, the visible open defect of naked eyes, and plate speed compared with
Small, Figure 11 is gained coating surface ESEM and energy spectrum diagram, by scanning figure it can be seen that coating surface is uneven, is had larger
Crystal grain is reunited, and containing impurity such as Si, C, O in coating it can be seen from energy spectrum diagram, and phosphorus content is relatively low, only 1.54wt%, this
It is probably because cement matrix is corroded in acid condition, is reacted with acid, therefore use has palladium activation method institute
It is poor to obtain coating performance.
Figure 12 is the Tafel curve comparison diagram for having coating obtained by palladium activation and no-palladium activating, as seen from the figure, using without palladium
The corrosion potential of coating is significantly greater than the corrosion potential for having coating obtained by palladium activation method obtained by activation method, illustrates no-palladium activating
Method is more suitable for cement base piezoelectric composite material chemical nickel plating on surface.
Comparative example 2
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 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：
Cement base piezoelectric composite material after roughening is put into reducing solution, soaks 10min, reducing solution at room temperature
For the pure methanol solution of sodium borohydride, the content of sodium borohydride is 70 g/L.
Step 4：With embodiment 1.
Step 5：With embodiment 1.
It is easy to volatilize as sodium borohydride solvent using pure methanol, not easy to operate, gained coating and basal body binding force are poor,
This is probably that sodium borohydride is active larger in pure methanol, and forming more active centre in matrix surface makes plating speed is excessive to make
Into, from visually, coating surface is uneven, and cement matrix and ceramic matrix have crack, and Figure 13 is coating surface morphology figure,
By it can also be seen that coating surface is uneven, there is larger crystal grain to reunite in figure, the crack in cement matrix and ceramic matrix is larger,
Do not covered by coating, therefore make sodium borohydride solvent using pure methanol to obtain coating of good performance.
Comparative example 3
To above-mentioned 8 × 8mm2, the cement base piezoelectric composite material surface that thickness is 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
For：Nickel sulfate 30g/L, trisodium citrate 20g/L, sodium hypophosphite 20g/L, the g/L of sodium acetate 12, borax 8g/L, use ammonia
Water adjustment pH is 6.5-7.5, and plating temperature is 45 DEG C.
Gained coating surface morphology is as shown in figure 14, and as seen from the figure, coating surface is uneven, out-of-flatness, and cement matrix
Exist with ceramic matrix intersection and accumulate and reunite compared with big crystal grain.In addition, the adhesion of coating is also poor, it is repeatedly right with 3M adhesive tapes
Coating surface is pasted, and coating surface has damaged and obscission after stickup.Therefore property of the selection of nickel-plating liquid for coating
There can be considerable influence.
Impossible to exhaust for embodiments of the present invention, example above is only that some embodiments of the present invention are arranged
Lift and illustrate, on the basis of above example, change the species of piezoelectric ceramics, epoxy resin and cement, change Piezoelectric anisotropy
The type of material can also obtain the good coating of effect.
Claims (13)
1. a kind of method in cement base piezoelectric composite material chemical nickel plating on surface, including to cement base piezoelectric composite material surface
Be roughened, reduced, being activated, Nickel Plating Treatment the step of, it is characterized in that：Roughening is carried out in alkaline coarsening solution, is reduced used
Reducing solution is the methanol aqueous solution of sodium borohydride or the ethanol water of sodium borohydride, and it is containing adding to activate activating solution used
Add the nickel acetate aqueous solution or nickel sulfate solution of agent, the additive is KI, lauryl sodium sulfate, ethylenediamine or poly-
Ethylene glycol, the nickel-plating liquid composition used in nickel plating are：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 6.5-7.5.
2. the method according to claim 11, it is characterized in that：The cement base piezoelectric composite material refer to using piezoelectric ceramics as
Functive, the piezo-electricity composite material formed using the mixture of epoxy resin and cement as matrix.
3. method according to claim 1 or 2, it is characterized in that：The compound method of coarsening solution is：By sodium hydroxide and carbonic acid
Sodium is with 5:1 mass ratio mixing, the aqueous solution of sodium carbonate and sodium hydroxide total mass fraction for 35wt% is made into, it is then molten to this
Potassium permanganate and ethylenediamine are added in liquid, makes potassium permanganate concentration be 5g/L, ethylenediamine concentration is 30mL/L, produces coarsening solution.
4. the method according to claim 11, it is characterized in that：In reducing solution, the content of sodium borohydride is 65-75 g/L.
5. the method according to claim 11, it is characterized in that：In reducing solution, methanol or the volume ratio of ethanol and water are 1:
1。
6. the method according to claim 11, it is characterized in that：The composition of activating solution be nickel acetate or nickel sulfate, additive and
Water, the additive are polyethylene glycol.
7. the method according to claim 1 or 6, it is characterized in that：In activating solution, the content of nickel acetate or nickel sulfate is 5-55
g/L；The content of additive is 20-30mg/L.
8. the method according to claim 11, it is characterized in that：In activating solution, the content of nickel acetate or nickel sulfate is 25-35g/
L。
9. the method according to claim 11, it is characterized in that：In activating solution, the content of nickel acetate or nickel sulfate is 25g/L.
10. the method according to claim 11, it is characterized in that：Roughening is carried out at 30 DEG C；Reduction is carried out at room temperature；It is living
Change is carried out at 25 DEG C -40 DEG C；Nickel plating is carried out at 45-50 DEG C.
11. the method according to claim 11, it is characterized in that：Activation is carried out at 35 DEG C；Nickel plating is carried out at 45 DEG C.
12. according to the method described in claim 1,10 or 11, it is characterized in that：Coarsening time is 30min, reduction and activation when
Between be 10min.
13. according to the method for claim 1, it is characterized in that, comprise the following steps：
（1）Cement base piezoelectric composite material surface is polished and oil removing；
（2）Cement base piezoelectric composite material after oil removing is placed in coarsening solution and carries out roughening treatment, water rinses after processing；
（3）Cement base piezoelectric composite material after roughening is put into reducing solution and carries out reduction treatment, the cement base after reduction
Piezo-electricity composite material, which places into, carries out activation process in activating solution；
（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, coating reaches
Stop nickel plating during to required thickness, produce nickel coating.
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