Process method for chemically plating nickel-phosphorus alloy on SMC material surface
Technical Field
The invention relates to the technical field of SMC material surface treatment, in particular to a process method for chemically plating a nickel-phosphorus alloy on the surface of an SMC material and application thereof.
Background
SMC (Sheet molding compound) material is a Sheet molding compound, mainly consists of glass fibers, unsaturated resin, filler, additives and auxiliaries, belongs to thermosetting resin-based composite materials, adopts a hot die cold pressing molding process for product molding, has the characteristics of excellent electrical insulation, light weight, high strength, flame retardance, no toxicity and the like, is widely applied to various fields of transportation, construction, electrical, communication, catering and the like, and is the most applied in the automobile industry.
The production process of SMC material consists of two stages of mould pressing material production and mould pressing process, the mould pressing material stage is that all the components except fibre are mixed together to make paste, then these paste are used to impregnate fibre so as to obtain the invented sheet moulding material. The sheet molding compound is made into a product through the working procedures of shearing, charging, compression molding, post-treatment and the like. As the fillers of calcium carbonate, hydrated alumina, magnesium oxide, talcum powder and the like are added into the mould pressing material, the SMC material has poor wear resistance and corrosion resistance, weak impact resistance and no conductivity at all.
The SMC material is non-conductive, wear-resistant and corrosion-resistant, so that the thin-wall product is easy to break and damage when being impacted by external force, further application is limited, if metal or alloy is plated on the surface of the SMC material to modify the surface of the SMC material, the wear-resistant, corrosion-resistant and impact-resistant properties are improved on the basis of keeping the original characteristics, the service life is prolonged, the SMC material is used as a conductive material, and the application field of the SMC material is wider.
Therefore, a method for modifying the surface of an SMC product by using a non-metallic material is needed to be constructed, so that the function of the SMC product is improved, although many methods for modifying the surface of the non-metallic material are available, such as vacuum plating, ion sputtering, spraying and the like, a chemical plating layer is uniform in thickness, high in hardness, good in wear resistance and corrosion resistance, even for a device with a complex structural shape, a layer of uniform metal or alloy can be plated on the surface of the non-metallic material, and an important method for modifying the surface of the non-metallic material is provided.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a process method for chemically plating a nickel-phosphorus alloy on the surface of an SMC material, a material prepared by the method and application of the material.
Chemical plating is also called autocatalytic plating, and is a process method for carrying out selective reduction deposition on metal ions in a solution on the surface of a base material presenting catalytic activity centers by using an oxidation-reduction reaction carried out in the plating process under the condition that no external current passes through, so that a metal alloy plating layer is formed on the surface of the base material, and the surface of the base material is modified, wherein the plated base material shows excellent performance in many aspects.
A process method for chemically plating a nickel-phosphorus alloy on the surface of an SMC material comprises the following steps:
(1) pretreatment of a plated part:
polishing the surface of the SMC material to be plated, soaking the SMC material in 1mol/L sodium carbonate solution, heating to 40 ℃, soaking for 10min, removing oil stains and glue films on the surface of the SMC material, and cleaning the SMC material by using distilled water;
(2) sensitization treatment:
placing the pretreated SMC material to be plated in a sensitizing solution, and treating for 5min at 30 ℃ to ensure that Sn is easily reduced by adsorption on the surface of a base material2+Taking out the base material and cleaning the base material by using distilled water;
(3) activation treatment:
putting the sensitized SMC material to be plated into activating solution, and utilizing Sn adsorbed on the surface of the base material2+Pd is added2+Reducing the metal Pd to form metal Pd particle catalytic crystallization centers; treating in activating solution at 40 deg.C for 10 min;
(4) reduction treatment:
the activated and uncleaned SMC material to be plated is put into 18g/L sodium hypophosphite solution for reduction treatment, the reduction treatment is carried out for 2min at the temperature of 30 ℃, and the strong reducing capability of the sodium hypophosphite is utilized to lead the unreduced Pd on the surface of the base material2+Completely reducing, taking out the SMC material, and washing the SMC material with distilled water;
(5) plating:
selecting a proper nickel-phosphorus alloy plating container according to the area of the SMC material, pouring the plating solution A and then pouring the plating solution B, and adjusting the pH value by using strong ammonia water or hydrochloric acid; as long as the plating solution B is poured into the plating solution A, the oxidation-reduction reaction is immediately carried out, so that after the plating solution B is poured into the plating solution A, the SMC material after reduction treatment is immediately put into the plating solution, and the plating loading is controlled to be 1.0-1.5 dm2Controlling the temperature and pH value of the plating solution, carrying out chemical nickel-phosphorus alloy plating, continuously stirring in the plating process to ensure that the concentration of the plating solution is uniform, enabling bubbles generated in the chemical plating process to escape, and controlling the plating time to be 40 min;
(6) treatment of
And (4) taking out the SMC plated part after plating is finished, washing the SMC plated part with absolute ethyl alcohol, removing impurities deposited on the surface of the plated part, and drying the SMC plated part.
Preferably, in the step (2), the sensitizing solution is 6g SnCl2After dissolving in 20ml concentrated hydrochloric acid, diluting to 500ml with distilled water, and adding prepared SnCl2Tin particles added to the solution to prevent Sn2+And (4) oxidizing.
Preferably, in the step (3), the activating solution is prepared by completely dissolving 0.5g of palladium chloride in 6ml of concentrated hydrochloric acid and then diluting the solution to 500ml with distilled water.
Preferably, in the step (5), the chemical plating solution preparation method comprises: accurately weighing various substances according to the composition of the plating solution, and removing NaH2PO2·H2O, respectively, with a small amount of distilled waterDissolving various substances, sequentially adding buffer (sodium acetate), complexing agent (succinic acid, citric acid), stabilizer, etc. solution into NiSO4·6H2Stirring the solution O uniformly to obtain a plating solution A; then adding a reducing agent NaH2PO2·H2Dissolving O alone to be used as plating solution B; controlling the volume of the plating solution according to the formula requirement of the chemical plating solution, and diluting the plating solution to the required volume by using distilled water.
Preferably, the process conditions of chemically plating the nickel-phosphorus alloy on the surface of the SMC material are as follows: the temperature of the plating solution is controlled to be 65 (+ -5) DEG C, and the pH value is 4.5-5.0.
Preferably, the process conditions of chemically plating the nickel-phosphorus alloy on the surface of the SMC material are as follows: ni2+/H2PO2 -The molar concentration ratio is 0.35 (+ -0.05), and the plating time is 40 (+ -10) min.
Preferably, it is characterized in that the first and second parts,
the preparation method of the chemical plating solution comprises the following steps: NiSO4·6H2O 24g/L,NaH2PO2·H2O28g/L,CH3COONa26g/L,C4H6O4(succinic acid) 15g/L, C6H8O7·H2O (citric acid) 10g/L and a small amount of stabilizer.
Preferably, the chemical reaction formula carried out during the plating process is:
3H2PO2 -+2H+→2P↓+3H2PO3 -+3H2O
H2PO2 -+H2O→H2PO3 -+H2↑
the invention also provides a material prepared by the process method for chemically plating the nickel-phosphorus alloy on the surface of the SMC material.
A material prepared by a process method for chemically plating a nickel-phosphorus alloy on the surface of an SMC material is applied to the fields of conductive materials, engineering materials, functional materials and the like.
The invention has the advantages that:
(1) the chemical nickel-phosphorus plating alloy is adopted to ensure that the surface coating of the SMC material is compact, uniform and bright
(2) Improve the wear resistance and corrosion resistance of SMC material
(3) The SMC material has enhanced conductive capability and can be used as a conductive material
(4) Broadens the application field of SMC material and has better economic benefit
Drawings
FIG. 1 is a block diagram of a chemical nickel-phosphorus alloy plating process for the surface of SMC material
FIG. 2 is a graph showing the results of experiments on the influence of plating solution temperature on plating quality
FIG. 3 is a graph showing the results of experiments on the influence of pH value of plating solution on the quality of plating layer
FIG. 4 Ni2+/H2PO2 -Experimental result chart of influence of molar concentration ratio on coating quality
FIG. 5 is a numerical chart of friction test of SMC plated and unplated parts
FIG. 6 is a graph showing the results of an experiment on the conductivity of SMC plated parts
FIG. 7 is a graph showing the results of an experiment on the conductivity of an SMC uncoated part
FIG. 8 plan view of a field scanning electron microscope for a plated part
FIG. 9 side view of a scanning electron microscope for a plating field
FIG. 10 Transmission Electron microscopy of plated parts
FIG. 11 Transmission Electron micrograph of plated part
Detailed Description
The following examples of the present invention are merely illustrative of specific embodiments for carrying out the present invention and are not to be construed as limiting the invention. Other changes, modifications, substitutions, combinations, and simplifications which may be made without departing from the spirit and principles of the invention are intended to be equivalent substitutions and are within the scope of the invention.
The basic steps of the process method for chemically plating the nickel-phosphorus alloy on the surface of the SMC material are as follows, and the subsequent process condition experiments are all tested on the basis.
(1) Pretreatment of a plated part:
polishing the surface of the SMC material to be plated, soaking the SMC material in 1mol/L sodium carbonate solution, heating to 40 ℃, soaking for 10min, removing oil stains and glue films on the surface of the SMC material, and cleaning the SMC material by using distilled water;
(2) sensitization treatment:
placing the pretreated SMC material to be plated in a sensitizing solution, and treating for 5min at 30 ℃ to ensure that Sn is easily reduced by adsorption on the surface of a base material2+Taking out the base material and cleaning the base material by using distilled water;
(3) activation treatment:
putting the sensitized SMC material to be plated into activating solution, and utilizing Sn adsorbed on the surface of the base material2+Pd is added2+Reducing the metal Pd to form metal Pd particle catalytic crystallization centers; treating in activating solution at 40 deg.C for 10 min;
(4) reduction treatment:
the activated and uncleaned SMC material to be plated is put into 18g/L sodium hypophosphite solution for reduction treatment, the reduction treatment is carried out for 2min at the temperature of 30 ℃, and the strong reducing capability of the sodium hypophosphite is utilized to lead the unreduced Pd on the surface of the base material2+ completely reducing, taking out SMC material and washing with distilled water;
(5) plating:
selecting a proper nickel-phosphorus alloy plating container according to the area of the SMC material, pouring the plating solution A and then pouring the plating solution B, and adjusting the pH value by using strong ammonia water or hydrochloric acid; as long as the plating solution B is poured into the plating solution A, the oxidation-reduction reaction is immediately carried out, so that after the plating solution B is poured into the plating solution A, the SMC material after reduction treatment is immediately put into the plating solution, and the plating loading is controlled to be 1.0-1.5 dm2Controlling the temperature and pH value of the plating solution, carrying out chemical nickel-phosphorus alloy plating, continuously stirring in the plating process to ensure that the concentration of the plating solution is uniform, enabling bubbles generated in the chemical plating process to escape, and controlling the plating time to be 40 min;
(6) treatment of
And (4) taking out the SMC plated part after plating is finished, washing the SMC plated part with absolute ethyl alcohol, removing impurities deposited on the surface of the plated part, and drying the SMC plated part.
Experiment of technological condition for chemical plating of nickel-phosphorus alloy on SMC material surface
The factors influencing the quality of the nickel-phosphorus alloy plating layer on the surface of the SMC material are more, such as the temperature of the plating solution, the pH value of the plating solution and Ni2+/H2PO2 -The mol concentration ratio, the complexing agent selection and the like, and the process flow and the operating conditions of chemically plating the nickel-phosphorus alloy on the surface of the SMC material are determined through a plurality of experimental researches: the temperature of the plating solution is controlled to be 65 +/-5 ℃, the pH value is 4.5-5.0, and Ni is added2+/H2PO2 -The molar concentration ratio is 0.35 (+ -0.05), the plating time is 40 (+ -10) min, and a dense, uniform and bright Ni-P alloy plating layer can be obtained.
Example 1
Experiment of influence of plating solution temperature on plating quality
Experiments show that when the temperature of the plating solution is lower than 35 ℃, the plating is difficult to apply, when the temperature of the plating solution is higher than 45 ℃, more bubbles appear on the surface of a plated part, the deposition speed of the nickel-phosphorus alloy is accelerated, when the plating solution is heated to be higher than 80 ℃, the plating solution begins to be turbid, the stability of the plating solution is poor, the binding force of the plating layer is weakened, the weight increasing rate of the plating layer is continuously increased from 45 ℃ to higher than 80 ℃, the increase is faster below 65 ℃, and the increase is slowed when the temperature is higher than 65 ℃. The result shows that the plating temperature is preferably controlled to be about 65 ℃. The results of the experiment are shown in FIG. 2.
Example 2
Experiment of influence of pH value of plating solution on quality of plating layer
Experiments show that the lower the pH value of the plating solution is, the lower the deposition rate of the nickel-phosphorus alloy is, and when the pH value of the plating solution is less than 3, the deposition reaction is stopped, so that the plating cannot be effectively carried out; the higher the pH value of the plating solution is, the higher the deposition speed is, the higher the weight gain rate of the plating layer is, but in the plating solution
And Ni
2+The formation of nickel phosphite or nickel hydroxide precipitates tends to make the bath turbid, and the coating becomes rough and carries with it the precipitates in the bath for codeposition, making the binding force of the coating poor and easily inducing the decomposition of the bath. The result shows that the pH value of the plating solution is preferably controlled to be 4.5-5.0. As shown in fig. 3.
Example 3
Ni2+/H2PO2 -Experiment of influence of molar concentration ratio on coating quality
Experiments show that the influence of sodium hypophosphite on the deposition speed and the quality of a coating is more obvious compared with the main salt nickel sulfate, when the content of the sodium hypophosphite in the plating solution is lower than 30g/L, the deposition speed is rapidly increased along with the increase of the content of the sodium hypophosphite, and when the content of the sodium hypophosphite in the plating solution exceeds 30g/L, the deposition speed is reduced. Ni2+/H2PO2 -When the ratio is less than 0.25, the plating layer becomes dark; ni2+/H2PO2 -When the ratio is more than 0.6, the deposition rate is low, and the plating is difficult. The results show that Ni2+/H2PO2 -When the ratio is controlled to be about 0.35, the deposition rate of the nickel-phosphorus alloy is high, and a uniform and bright coating can be obtained. The results of the experiment are shown in FIG. 4.
Example 3
Test of influence of other factors on coating quality
Experiments show that when the plating solution is added into the sodium hypophosphite solution, oxidation-reduction reaction can occur, if the substrate is not added (namely, no-load) for too long time, nickel ions are reduced to form nickel particles, so that the plating solution is decomposed, and therefore, the plating solution is put into the substrate for plating as soon as possible after the sodium hypophosphite is added into the plating solution. In addition, the addition and selection of the complexing agent also influence the deposition speed and the coating quality of the nickel-phosphorus alloy, the complexing agent succinic acid and citric acid are multifunctional complexing agents and form a complex with nickel ions, the reaction concentration of the nickel ions in the plating solution is controlled, and the succinic acid has the effects of reducing the precipitation reaction activation energy of the nickel-phosphorus alloy and accelerating the deposition speed, so that the content of the succinic acid in the plating solution can be neither excessive nor too low.
The following tests are adopted to verify the effect of the invention:
and chemically plating the nickel-phosphorus alloy on the surface of the SMC material according to the control conditions of the process for chemically plating the nickel-phosphorus alloy on the surface of the SMC material, and selecting a plated part to carry out performance detection.
First wear resistance test
Selecting SMC plated piece and non-plated piece, accurately weighing, and respectively placing in standard NO.180#Water-resistant sandAnd (3) placing a 100g weight on the paper, pushing along the length of the long edge of the abrasive paper to perform a wear resistance test, recording the friction times and the quality of the sample, calculating the friction loss rate, and obviously improving the wear resistance of the plated part compared with the non-plated part. The results of the experiment are shown in FIG. 5.
w1- -mass of sample before rubbing, g
w2- -mass of sample after abrasion, g
A conductivity test
The CHI660E electrochemical workstation is used for detecting the conductivity of the SMC plated part and the non-plated part, and the result shows that the impedance value of the non-plated part is large, the non-conductive capacity is high, the impedance value of the plated part is small, the conductivity is good, and the SMC plated part can be used as a conductive material. The experimental test results are shown in fig. 6 and 7.
Corrosion resistance test of the third product
Respectively putting the SMC plated part and the non-plated part into different solutions to soak for a certain time for corrosion resistance experimental detection, recording the mass loss of the SMC plated part and the non-plated part in different solutions and different soaking times, and calculating the corrosion rates of the plated part and the non-plated part, wherein the experimental result shows that the corrosion resistance of the plated part is enhanced compared with that of the non-plated part. The corrosion results of the plated and non-plated parts in various solutions at 25 ℃ are shown in Table 1.
w1- -mass of sample before Corrosion, g
w2- -mass of sample after Corrosion, g
TABLE 125 ℃ Corrosion results of plated articles in various solutions
Fourth step, detection of scanning electron microscope and transmission electron microscope
The SMC plated part is detected by a field emission scanning electron microscope Sigma 500VP (ZEISS German Zeiss), the plating layer is compact, bright and uniform, and the thickness of the plating layer is more than 10 mu m; the JEM-2100PLUS transmission electron microscope (JEOL company) detects that the diffraction pattern has no lattice fringes and no diffraction light spots around the diffraction ring, which shows that the nickel-phosphorus alloy of the SMC plating piece is in an amorphous structure, and the structure is favorable for improving the wear resistance and the corrosion resistance of the plating piece. The test results are shown in fig. 8, 9, 10, and 11 below.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.