CN104016593B - At the chemical plating method of glass microballon or fiberglass surfacing clad metal cobalt - Google Patents
At the chemical plating method of glass microballon or fiberglass surfacing clad metal cobalt Download PDFInfo
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Abstract
The present invention relates to a kind of chemical plating method at glass microballon and fiberglass surfacing clad metal cobalt, mainly comprise the following steps: first by preprocessing process, surface treatment is carried out to glass microballon and glass fibre, to give its surface certain catalytic activity, concrete preprocessing process comprises degreasing (only for glass fibre), alligatoring, sensitization and activation step.Then adopt chemical plating method through pretreated glass microballon or fiberglass surfacing metallizing cobalt, made nucleocapsid structure composite particles has excellent electricity-magnetic bi-functional concurrently.By changing main salt, complexing agent, reductive agent consumption and the processing parameter such as plating temperature and time in chemical plating fluid, sedimentation velocity and the thickness of coating can be controlled, thus realize the regulation and control to composite particles conductivity and microscopic appearance.
Description
Technical field
The present invention relates to the preparation method of the micro-nano composite particles of shell-core structure, be specially a kind of electroless cobalt plating method at glass microballon or fiberglass surfacing clad metal cobalt.
Background technology
The micro-nano composite particles of shell-core structure is because having the multiple performance of shell and core sill concurrently, often integrate optical, electrical, two or more performance such as magnetic and heat, its synergistic effect all has very wide application prospect in fields such as catalysis, drug conveying, functional stuffing, photoelectric material, magneticsubstances.The method preparing the micro-nano composite particles of shell-core structure is a lot, as self-assembly method, vapour deposition process, electrochemical process, situ aggregation method, electroless plating method etc.G.Sreenivasulu etc. [G.Sreenivasulu, Appl.Phys.Lett., 2014,104,052910] adopt magnetic field assisted self assembling legal system for shell-core structure ferroelectric material; [F.B.Su, etal, the J.Mater.Chem. such as F.B.Su, 2006,16:4413-4419] be first template with silicon dioxide microsphere, adopt vapor phase deposition method (CVD) at the presoma of its surface deposition benzene material as carbon, final synthesis single dispersing hollow carbon balls; V.Mancier etc. [V.Mancier, etal, Ultrason.Son DEG C of hem., 2010,17:690-696.] adopt electrochemical method to prepare Ag/Cu shell-core structure conducting particles; Y.G.Wang etc. [Y.G.Wang, etal., Angew.Chem.Int.Edit., 47:7461 – 7465.] adopt situ aggregation method to prepare LiFePO4/Carbo shell-core structure composite particles, wherein nuclear matter LiFePO
4have good degree of crystallinity, be of a size of 20-40nm, shell is the translucent carbon material of thickness 1-2nm, and this method can be widely used in the preparation of other shell-core structure matrix materials; W.Z.Li etc. [W.Z.Li, ACSAppl.Mater.Interfaces., 2013, the 5:883-891.] polystyrene/Ni lightweight Electromagnetic heating microballoon that adopted chemical plating method to prepare.
Prepare in the method for the micro-nano composite particles of shell-core structure numerous, electroless plating is a kind of simple, with low cost, method that practicality is wider.In recent years, adopt the research of chemical plating method metallizing on the matrixes such as metal, polymkeric substance and inorganic powder more, no matter be sheet material, bar, complex-shaped profiled material or dusty material, smooth and the matrix material of densification of coating can be obtained, and plating metal expands to the metals such as Co, Ag, Au, Pd gradually from traditional Ni, Cu, matrix material obtains applying more widely in fields such as electron device, aviation and navigations.
Summary of the invention
The object of the present invention is to provide a kind of electroless cobalt plating method at glass microballon or fiberglass surfacing clad metal cobalt, there is the features such as low density, low cost and good dispersion.
The present invention adopts following technical scheme to realize:
In an electroless cobalt plating method for glass microballon or fiberglass surfacing clad metal cobalt, comprise the steps:
(1), pre-treatment is carried out to glass microballon or fiberglass surfacing:
The surface preparation of glass microballon comprises the following steps: (a), alligatoring: joined by glass microballon in coarsening solution, temperature 28 ~ 32 DEG C, stirs 10 ~ 20min, washs for subsequent use; (b), sensitization: the glass microballon through roughening treatment is joined in sensitizing solution, temperature 28 ~ 32 DEG C, stirs 10 ~ 20min, washs for subsequent use; C (), activation: join in activation solution by the glass microballon entering sensitization plays process, temperature 28 ~ 32 DEG C, stir 10 ~ 20min, wash for subsequent use;
The pre-treatment of glass fibre comprises the following steps: (I), join in skim soln by glass fibre, temperature 65 ~ 75 DEG C, stirs 1.5 ~ 2.5h, after washing, and dry for standby; (II), carry out alligatoring, sensitization and activation treatment successively through the glass fibre of skimming treatment, specific operation process is with above glass microballon (a) ~ (c) step;
Specifically consisting of of described coarsening solution: the vitriol oil 50 ~ 100mL/L of potassium bichromate 20 ~ 50g/L, 98wt%, solvent is distilled water;
Specifically consisting of of described sensitizing solution: the hydrochloric acid 10mL/L of tin protochloride 20g/L, 37wt%, solvent is distilled water;
Specifically consisting of of described activation solution: the hydrochloric acid 1mL/L of Palladous chloride 0.1 ~ 0.5g/L, 37wt%, solvent is distilled water;
(2), the preparation process of Co/ glass microballon nucleocapsid structure composite particles: pretreated glass microballon is distributed in the container filling electroless cobalt plating solution (A liquid), when being then heated to 40 ~ 90 DEG C, drip reductive agent (B liquid) and form plating solution (its volume equals A liquid and adds B liquid) afterwards, after reaction 10 ~ 120min, washing, suction filtration, oven dry;
The preparation process of Co/ glass fibre nucleocapsid structure composite particles: pretreated glass fibre is distributed in the container filling electroless cobalt plating solution (A liquid), when being then heated to 30 ~ 90 DEG C, drip reductive agent (B liquid) and form plating solution (its volume equals A liquid and adds B liquid) afterwards, after reaction 10 ~ 120min, washing, suction filtration, oven dry;
Described reductive agent is ortho phosphorous acid sodium solution.
The CoC of specifically consisting of of described plating solution: 5 ~ 35g/L
l26H
2the Trisodium Citrate of O, 30 ~ 100g/L, the ammoniacal liquor 20 ~ 240mL/L of 25wt%, the inferior sodium phosphate of 5 ~ 60g/L, solvent is distilled water.
The process for preparation of described electroless cobalt plating solution is specially: take 0.5 ~ 3.5g metal-salt CoCl
26H
2the complexing agent Trisodium Citrate of O and 3 ~ 10g, joins in a small amount of distilled water successively, adds the ammoniacal liquor 2 ~ 24mL of 25wt%, be then settled to 90mL with distilled water after stirring and dissolving, forms A liquid.
The layoutprocedure of described reductant solution is specially: take 0.5 ~ 6g inferior sodium phosphate, is dissolved in the distilled water of 10mL, stirs, and after fully dissolving, forms B liquid.
The present invention is intended to adopt chemical plating method at glass microballon or fiberglass surfacing cobalt plating respectively, first by preprocessing process, surface treatment is carried out to glass microballon and glass fibre, to give its surface certain catalytic activity, concrete preprocessing process comprises degreasing (only for glass fibre), alligatoring, sensitization and activation step; Then adopt chemical plating method through pretreated glass microballon or fiberglass surfacing metallizing cobalt, made nucleocapsid structure composite particles has excellent electricity-magnetic bi-functional concurrently.By changing main salt, complexing agent, reductive agent consumption and the processing parameter such as plating temperature and time in chemical plating fluid, sedimentation velocity and the thickness of coating can be controlled, thus realize the regulation and control to composite particles conductivity and microscopic appearance.Wherein, glass microballon and glass fibre carry out pretreated coarsening solution, sensitizing solution, activation solution preparation also very crucial, the pretreating effect of different preprocessing solutions to glass microballon and glass fibre is significantly different, also the Chemical bond of cobalt metal at glass microballon and glass fibre is directly affected, i.e. the quality of nucleocapsid structure composite particles.
The present invention is reasonable in design, adopt chemical plating method at glass microballon or fiberglass surfacing cobalt plating respectively, the shell-core structure composite particles obtaining electromagnetic performance excellence has the features such as low density, low cost and good dispersion, can as a kind of filler of conductive rubber, be applied in electromagnetic shielding field, with technical requirementss such as satisfied contemporary lightweight, efficient, widescreen shieldings.
Accompanying drawing explanation
Fig. 1 represents the SEM picture of Co/ glass microballon shell-core structure composite particles in embodiment 1.
Fig. 2 is the partial enlarged drawing of Fig. 1.
Fig. 3 represents the XRD figure spectrum of Co/ glass microballon shell-core structure composite particles corresponding in embodiment 1.
Fig. 4 represents Co/ glass microballon shell-core structure composite particles VSM graphic representation corresponding in embodiment 1.
Fig. 5 is the partial enlargement graphic representation of Fig. 4.
Fig. 6 represents the SEM picture of Co/ glass microballon shell-core structure composite particles in embodiment 2.
Fig. 7 is the partial enlarged drawing of Fig. 6.
Fig. 8 represents the SEM picture of Co/ glass microballon shell-core structure composite particles in embodiment 3.
Fig. 9 is the partial enlarged drawing of Fig. 8.
Figure 10 represents the SEM picture of Co/ glass fibre shell-core structure composite particles in embodiment 4.
Figure 11 is the partial enlarged drawing of Figure 10.
Figure 12 represents the SEM picture of Co/ glass fibre shell-core structure composite particles in embodiment 5.
Figure 13 is the partial enlarged drawing of Figure 12.
Figure 14 represents the SEM picture of Co/ glass fibre shell-core structure composite particles in embodiment 6.
Figure 15 is the partial enlarged drawing of Figure 14.
Embodiment
Below specific embodiments of the invention are described in detail.
embodiment 1
In an electroless cobalt plating method for glass microballon surface clad cobalt, comprise the steps:
(1) glass microballon surface preparation:
Taking 3g glass microballon joins in the coarsening solution of 100mL, and constant temperature 28 DEG C, at the uniform velocity stirs 12min, suction filtration, joins in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 30 DEG C, at the uniform velocity stir 15min, suction filtration, joins in the activation solution of 100mL with after distilled water wash 2 times, constant temperature 31 DEG C, after at the uniform velocity stirring 17min, suction filtration, with distilled water wash, for subsequent use.
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 30g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 60mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution.
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join.
Activation solution: the PdCl taking 0.1g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h.
(2) preparation of Co/ glass microballon shell-core structure composite particles
Take 3g cobalt chloride and 4g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 12mL of 25wt%, then be settled to 90mL with distilled water, afterwards the glass microballon of above-mentioned process joined in the solution of preparation as A liquid; Take 1.5g inferior sodium phosphate subsequently, be dissolved in the distilled water of 10mL, stir, as reduced liquid B liquid after fully dissolving.Be placed in water-bath by the beaker filling A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 90 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 30g/L
l26H
2the Trisodium Citrate of O, 40g/L, the ammoniacal liquor 120mL/L of 25wt%, the inferior sodium phosphate of 15g/L, solvent is distilled water.Termination reaction after Keep agitation 50min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass microballon shell-core structure composite particles.
The volume resistivity value of the Co/ glass microballon shell-core structure composite particles of the present embodiment is in table 1; Fig. 1,2 is shown in by the SEM picture of Co/ glass microballon shell-core structure composite particles; The XRD figure spectrum of Co/ glass microballon shell-core structure composite particles is shown in Fig. 3; The VSM curve of Co/ glass microballon shell-core structure composite particles is shown in Fig. 4,5.
embodiment 2
In an electroless cobalt plating method for glass microballon surface clad cobalt, comprise the steps:
(1) glass microballon surface preparation
Taking 3g glass microballon joins in the coarsening solution of 100mL, and constant temperature 32 DEG C, at the uniform velocity stirs 15min, suction filtration, joins in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 29 DEG C, at the uniform velocity stir 20min, suction filtration, joins in the activation solution of 100mL with after distilled water wash 2 times, constant temperature 30 DEG C, after at the uniform velocity stirring 16min, suction filtration, with distilled water wash, for subsequent use.
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 20g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 80mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution.
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join.
Activation solution: the PdCl taking 0.2g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h.
(2) preparation of Co/ glass microballon shell-core structure composite particles
Take 2.5g cobalt chloride and 8g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 10mL of 25wt%, then be settled to 90mL with distilled water, afterwards the glass microballon of above-mentioned process joined in the solution of preparation as A liquid; Take 0.5g inferior sodium phosphate, be dissolved in the distilled water of 10mL, stir, as reduced liquid B liquid after fully dissolving.Be placed in water-bath by the beaker filling A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 70 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 25g/L
l26H
2the Trisodium Citrate of O, 80g/L, the ammoniacal liquor 100mL/L of 25wt%, the inferior sodium phosphate of 5g/L, solvent is distilled water.Termination reaction after Keep agitation 30min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass microballon shell-core structure composite particles.
The volume resistivity value of the Co/ glass microballon shell-core structure composite particles of the present embodiment is in table 1; Fig. 6,7 is shown in by the SEM picture of Co/ glass microballon shell-core structure composite particles.
embodiment 3
In an electroless cobalt plating method for glass microballon surface clad cobalt, comprise the steps:
(1) glass microballon surface preparation
Taking 3g glass microballon joins in the coarsening solution of 100mL, and constant temperature 30 DEG C, at the uniform velocity stirs 10min, suction filtration, joins in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 29 DEG C, at the uniform velocity stir 15min, suction filtration, joins in the activation solution of 100mL with after distilled water wash 2 times, constant temperature 32 DEG C, after at the uniform velocity stirring 18min, suction filtration, with distilled water wash, for subsequent use.
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 25g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 100mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution.
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join.
Activation solution: the PdCl taking 0.3g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h.
(2) preparation of Co/ glass microballon shell-core structure composite particles
Take 1g cobalt chloride and 5g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 20mL of 25wt%, then be settled to 90mL with distilled water, afterwards the glass microballon of above-mentioned process joined in the solution of preparation as A liquid; Take 3g inferior sodium phosphate subsequently, be dissolved in the distilled water of 10mL, stir after fully dissolving as reduced liquid B liquid.Be placed in water-bath by the beaker containing A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 40 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 10g/L
l26H
2the Trisodium Citrate of O, 50g/L, the ammoniacal liquor 200mL/L of 25wt%, the inferior sodium phosphate of 30g/L, solvent is distilled water.Termination reaction after Keep agitation 120min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass microballon shell-core structure composite particles.
The volume resistivity value of the Co/ glass microballon shell-core structure composite particles of the present embodiment is in table 1; Fig. 8,9 is shown in by the SEM picture of Co/ glass microballon shell-core structure composite particles.
embodiment 4
In an electroless cobalt plating method for fiberglass surfacing clad metal cobalt, comprise the steps:
(1) fiberglass surfacing pre-treatment
The preprocessing process of glass fibre: first need to carry out skimming treatment, joins 200g glass fibre in the NaOH solution (NaOH of 30g/L) of 600mL, is heated to 70 DEG C, after constant temperature at the uniform velocity stirs 2h, with distilled water wash, in the baking oven of 80 DEG C, dry 4h, for subsequent use; Then taking 3g glass fibre joins in the coarsening solution of 100mL, and constant temperature 31 DEG C, at the uniform velocity stirs 20min, suction filtration, joins in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 28 DEG C, at the uniform velocity stir 15min, suction filtration, joins in the activation solution of 100mL with after distilled water wash 2 times, constant temperature 30 DEG C, after at the uniform velocity stirring 15min, suction filtration, with distilled water wash, for subsequent use.
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 35g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 70mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution.
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join.
Activation solution: the PdCl taking 0.4g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h.
(2) preparation of Co/ glass fibre shell-core structure composite particles
Take 0.5g cobalt chloride and 7g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 2mL of 25wt%, then be settled to 90mL with distilled water, afterwards the glass fibre of above-mentioned process joined in the solution of preparation as A liquid; Take 5.0g inferior sodium phosphate subsequently, be dissolved in the distilled water of 10mL, stir, as reduced liquid B liquid after fully dissolving.Be placed in water-bath by the beaker filling A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 30 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 5g/L
l26H
2the Trisodium Citrate of O, 70g/L, the ammoniacal liquor 20mL/L of 25wt%, the inferior sodium phosphate of 50g/L, solvent is distilled water.Termination reaction after Keep agitation 25min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass fibre shell-core structure composite particles.
The volume resistivity value of the Co/ glass fibre shell-core structure composite particles of the present embodiment is in table 1; Figure 10,11 is shown in by the SEM picture of Co/ glass fibre shell-core structure composite particles.
embodiment 5
In an electroless cobalt plating method for fiberglass surfacing clad metal cobalt, comprise the steps:
(1) fiberglass surfacing pre-treatment
The preprocessing process of glass fibre: first need to carry out skimming treatment, joins 200g glass fibre in the NaOH solution (NaOH of 30g/L) of 600mL, is heated to 65 DEG C, after constant temperature at the uniform velocity stirs 2.5h, with distilled water wash, in the baking oven of 80 DEG C, dry 4h, for subsequent use;
Then taking 3g degreasing glass fibre joins in the coarsening solution of 100mL, and constant temperature 29 DEG C, at the uniform velocity stirs 10min, suction filtration, joins in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 32 DEG C, at the uniform velocity stir 18min, suction filtration, joins in the activation solution of 100mL with after distilled water wash 2 times, constant temperature 30 DEG C, after at the uniform velocity stirring 15min, suction filtration, with distilled water wash, for subsequent use.
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 45g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 50mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution.
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join.
Activation solution: the PdCl taking 0.5g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h.
(2) preparation of Co/ glass fibre shell-core structure composite particles
Take 3.5g cobalt chloride and 3g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 24mL of 25wt%, then be settled to 90mL with distilled water, afterwards the glass fibre of above-mentioned process joined in the solution of preparation as A liquid; Take 6g inferior sodium phosphate subsequently, be dissolved in the distilled water of 10mL, stir, as reduced liquid B liquid after fully dissolving.Be placed in water-bath by the beaker filling A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 90 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 35g/L
l26H
2the Trisodium Citrate of O, 30g/L, the ammoniacal liquor 240mL/L of 25wt%, the inferior sodium phosphate of 60g/L, solvent is distilled water.Termination reaction after Keep agitation 00min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass fibre shell-core structure composite particles.
The volume resistivity value of the Co/ glass fibre shell-core structure composite particles of the present embodiment is in table 1; Figure 12,13 is shown in by the SEM picture of Co/ glass fibre shell-core structure composite particles.
embodiment 6
In an electroless cobalt plating method for fiberglass surfacing clad metal cobalt, comprise the steps:
(1) fiberglass surfacing pre-treatment
The preprocessing process of glass fibre: first need to carry out skimming treatment, joins 200g glass fibre in the NaOH solution (NaOH of 30g/L) of 600mL, is heated to 75 DEG C, after constant temperature at the uniform velocity stirs 1.5h, with distilled water wash, in the baking oven of 80 DEG C, dry 4h, for subsequent use;
Then taking 3g degreasing glass fibre joins in the coarsening solution of 100mL, and constant temperature 30 DEG C, at the uniform velocity stirs 16min, suction filtration, join in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 32 DEG C, at the uniform velocity stirs 18min, suction filtration, constant temperature 28 DEG C in the activation solution of 100mL is joined with after distilled water wash 2 times, after at the uniform velocity stirring 15min, suction filtration, with distilled water wash, for subsequent use.
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 50g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 90mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution.
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join.
Activation solution: the PdCl taking 0.1g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h.
(2) preparation of Co/ glass fibre shell-core structure composite particles
Take 1.5g cobalt chloride and 10.0g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 8mL of 25%, then be settled to 90mL with distilled water, afterwards the glass fibre of above-mentioned process joined in the solution of preparation as A liquid; Take 4.5g inferior sodium phosphate subsequently, be dissolved in the distilled water of 10mL, stir, as reduced liquid B liquid after fully dissolving.Be placed in water-bath by the beaker filling A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 50 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 15g/L
l26H
2the Trisodium Citrate of O, 100g/L, the ammoniacal liquor 80mL/L of 25wt%, the inferior sodium phosphate of 45g/L, solvent is distilled water.Termination reaction after Keep agitation 100min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass fibre shell-core structure composite particles.
The volume resistivity value of the Co/ glass fibre shell-core structure composite particles of the present embodiment is in table 1; Figure 14,15 is shown in by the SEM picture of Co/ glass fibre shell-core structure composite particles.
The volume resistivity value of composite particles corresponding in each embodiment is as table 1:
Table 1
Claims (1)
1., in an electroless cobalt plating method for glass microballon surface clad cobalt, it is characterized in that: comprise the steps:
(1) glass microballon surface preparation:
Taking 3g glass microballon joins in the coarsening solution of 100mL, and constant temperature 28 DEG C, at the uniform velocity stirs 12min, suction filtration, joins in the sensitizing solution of 100mL with after distilled water wash 2 times, constant temperature 30 DEG C, at the uniform velocity stir 15min, suction filtration, joins in the activation solution of 100mL with after distilled water wash 2 times, constant temperature 31 DEG C, after at the uniform velocity stirring 17min, suction filtration, with distilled water wash, for subsequent use;
Wherein, the composition of coarsening solution, sensitizing solution and activation solution and process for preparation as follows:
Coarsening solution: the potassium bichromate taking 30g joins in the large beaker that 1000mL distilled water is housed, then the vitriol oil of the 98wt% measuring 60mL slowly adds wherein while stirring, after particulate state potassium bichromate is dissolved completely, namely obtain coarsening solution;
Sensitizing solution: the SnCl taking 2g
2put in the beaker that 100mL distilled water is housed, drip the dense HCl of the 37wt% of 1mL wherein, stir until solution clarification, be sensitizing solution, each experiment needs now to join;
Activation solution: the PdCl taking 0.1g
2, be dissolved in the dense HCl of the 37wt% of 1mL, after stirring with glass stick, instillation fills in the large beaker of 1000mL distilled water, and after stirring, room temperature leaves standstill 2h;
(2) preparation of Co/ glass microballon shell-core structure composite particles
Take 3g cobalt chloride and 4g Trisodium Citrate, join in the beaker filling a small amount of distilled water successively, after stirring and dissolving, add the ammoniacal liquor 12mL of 25wt%, then be settled to 90mL with distilled water, afterwards the glass microballon of above-mentioned process joined in the solution of preparation as A liquid; Take 1.5g inferior sodium phosphate subsequently, be dissolved in the distilled water of 10mL, stir, as reduced liquid B liquid after fully dissolving;
Be placed in water-bath by the beaker filling A liquid and heat, stirring velocity is 300r/min, when temperature in beaker rises to 90 DEG C, dropwise adds B liquid, forms plating solution 100ml after all dripping, now specifically the consisting of of described plating solution: the CoC of 30g/L
l26H
2the Trisodium Citrate of O, 40g/L, the ammoniacal liquor 120mL/L of 25wt%, the inferior sodium phosphate of 15g/L, solvent is distilled water; Termination reaction after Keep agitation 50min, vacuum filtration, successively washs 3 times with distilled water and dehydrated alcohol, dry 2h at 80 DEG C respectively, obtains Co/ glass microballon shell-core structure composite particles.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410262463.5A CN104016593B (en) | 2014-06-13 | 2014-06-13 | At the chemical plating method of glass microballon or fiberglass surfacing clad metal cobalt |
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