CN101311308B - Five-component alloy plating solution for chemical plating on surface of fiberglass and method for preparing same - Google Patents

Abstract

The invention relates to a glass fiber electroless plating Ni-Co-Fe-La-P quinary alloy bath and the preparation method thereof, which is characterized in that the formula of the bath includes: nickel sulfate, cobalt sulfate, inferior sodium phosphate, ferrous sulfate, lanthanum oxide, sodium citrate, malic acid, succinic acid, ammonium sulfate, distilled water, thiourea, urea and concentrated hydrochloric acid. The preparation method is as follows: the main salt nickel sulfate, the cobalt sulfate and the ferrous sulfate are put in the distilled water; the lanthanum sesquioxide, the distilled water and the concentrated hydrochloric acid are added after being dissolved; the sodium citrate, the malic acid, the succinic acid, the ammonium sulfate, the inferior sodium phosphate, the thiourea and the urea are sequentially added into the distilled water and stirred until being completely dissolved; the ammonia is dropped in to make the electroless plating solution. The invention has the beneficial effects that: owing to the suitable amount of La2O3 added in the electroless plating solution, the phosphorous content of the made alloy cladding is 3 percent to 17 percent. The glass fiber adopting the electroless plating has good conductivity and can be used as conductive filler and electric loss absorbent.

Description

Five-component alloy plating solution for chemical plating on surface of fiberglass and preparation method thereof

Technical field

The present invention relates to a kind of five-component alloy plating solution for chemical plating on surface of fiberglass and preparation method thereof.

Background technology

At present, more to electroless plating ternary alloy plating solution and preparation method thereof report both at home and abroad, quaternary and quinary alloy plating bath are less with the report of relevant rare earth element electroless plating, and major part is carried out plating on metallic matrix.General add fashionablely when rare earth element, the stability of plating bath, sedimentation velocity and quality of coating can obviously improve, and material can be used for preparing magnetic recording media and corrosion-resistant coating, but only on metallic matrix plating limited the use range of material undoubtedly.In recent years, the widespread use in electronic industry of various non-metallic material, macromolecular material, and hertzian wave can pass through these materials unblockedly, causes serious electromagnetic pollution and leakage of information.For preventing electromagnetic pollution and information leakage, hertzian wave controlled with shielding processing seem particularly important, and when adopting metallic stuffing to make conductive filler material, have the shortcoming that price is more expensive, coating wt is bigger.

Summary of the invention

The technical problem that solves

For fear of the deficiencies in the prior art part, the present invention proposes a kind of five-component alloy plating solution for chemical plating on surface of fiberglass and preparation method thereof, with single nickel salt, rose vitriol and ferrous sulfate is main salt, inferior sodium phosphate is a reductive agent, Trisodium Citrate, oxysuccinic acid and Succinic Acid are compound complex agent, urea and thiocarbamide are one package stabilizer, and ammonium sulfate is buffer reagent, rare earth oxide La ₂O ₃, ammoniacal liquor and hydrochloric acid are feedstock production.

Technical scheme

A kind of fiberglass surfacing Ni-Co-Fe-La-P alloy electroplating bath is characterized in that the prescription of plating bath is:

Single nickel salt NiSO ₄6H ₂O:1.8～2.60g/100ml,

Rose vitriol CoSO ₄7H ₂O:0.6～1.80g/100ml,

Inferior sodium phosphate NaH ₂PO ₂H ₂O:2.1～3.50g/100ml,

Ferrous sulfate FeSO ₄7H ₂O:0.5～1.70g/100ml,

Lanthanum trioxide La ₂O ₃: 0.02～0.18g/100ml,

Trisodium Citrate Na ₃C ₆H ₅O ₇2H ₂O:3.0～3.50g/100ml,

Oxysuccinic acid C ₄H ₆O ₅: 0.8～1.70g/100ml,

Succinic Acid C ₄H ₆O ₄: 0.6～1.50g/100ml,

Ammonium sulfate (NH ₄) ₂SO ₄: 3.8～5.0g/100ml,

Distilled water H ₂O:100ml,

Thiocarbamide CH ₄N ₂S:o.oo8～0.05g/100ml,

Urea CO (NH ₂) ₂: 0.9～2.10g/100ml,

Concentrated hydrochloric acid HCl:2.5～5.50g/100ml.

A kind of method for preparing above-mentioned plating bath is characterized in that: the preparation process of described Ni-Fe-Co-La-P gold plating bath is as follows:

Step 1, main salt single nickel salt, rose vitriol and ferrous sulfate are put into beaker A, add the distilled water of 95ml;

Step 2, the lanthanum sesquioxide that takes by weighing is put into the B beaker, adds 5ml distilled water and concentrated hydrochloric acid, under the normal temperature in magnetic stirring apparatus stirring and dissolving, join after the dissolving in the A beaker;

Step 3, Trisodium Citrate, oxysuccinic acid, Succinic Acid, ammonium sulfate, inferior sodium phosphate, thiocarbamide and urea add among the beaker A successively, are stirred to fully dissolving, splash into ammoniacal liquor and regulate pH=8.0 ± 0.2, are made into chemical plating fluid.

Beneficial effect

Fiberglass surfacing Ni-Co-Fe-La-P alloy electroplating bath that the present invention proposes and preparation method thereof adds La in plating bath ₂O ₃, not only improve the stability and the utilization ratio of plating bath, and improved the content of metallic element Ni, Co, Fe in the alloy layer, and in alloy layer, introduced rare-earth elements La, greatly reduce phosphorus content, can also reduce the plating temperature of electroless plating simultaneously.In chemical plating fluid, add an amount of La ₂O ₃, in the obtained alloy layer phosphorus content 3%～17%, and tradition with the metal be in the electroless plating alloy layer of matrix phosphorus content 15%～30%; Glass fibre has good electrical conductivity, can be used as conductive filler material and electrical loss absorption agent and uses.

Description of drawings

Fig. 1: the SEM figure of fiberglass surfacing alloy layer

A: do not add La ₂O ₃

B: add La ₂O ₃

Fig. 2: the resistivity of amorphous alloy coating under the plated state

Embodiment

Now in conjunction with the accompanying drawings the present invention is further described:

Step 1, take by weighing the beaker that single nickel salt (2.10g), rose vitriol (1.10g), ferrous sulfate (0.80g) are put into 250ml, add the distilled water of 95ml.

Step 2, take by weighing the beaker that lanthanum sesquioxide (0.12g) is put into 50ml, add 5ml distilled water and 2.50～5.50ml concentrated hydrochloric acid, under the normal temperature in magnetic stirring apparatus stirring and dissolving, the dissolving back adds in above-mentioned 1 in the 250ml beaker.

Step 3, take by weighing Trisodium Citrate (3.50g), oxysuccinic acid (0.90g), Succinic Acid (0.60g), inferior sodium phosphate (3.0g), ammonium sulfate (4.10g), thiocarbamide (0.02g) and urea (1.35g) and add successively in the beaker of 250ml in above-mentioned 1, be stirred to dissolving fully, splash into ammoniacal liquor and regulate pH=8.0 ± 0.2, be made into chemical plating fluid.

Application Example of the present invention:

The glass fibre that pre-treatment is good is put into the above-mentioned chemistry that has prepared and is crossed liquid, and heating in water bath reacts 20～60min down at 50 ℃～70 ℃, after reaction finishes, take out glass fibre, clean 3 times with distilled water, handle dry half an hour in baking oven, and temperature is at 70 ± 5 ℃.

The characteristics that the Ni-Co-Fe-La-P chemical plating fluid of the present invention development carries out the conductive magneto-conductive glass fibre that electroless plating obtains are: (1) adds rare earth oxide La in plating bath ₂O ₃, not only improve the stability and the utilization ratio of plating bath, and improved the content of metallic element Ni, Co, Fe in the alloy layer, and in alloy layer, introduced rare-earth elements La, reduce P content greatly, in chemical plating fluid, add an amount of La ₂O ₃, phosphorus content is 3%～17% in the obtained alloy layer, and tradition is that phosphorus content is 15%～30% in the electroless plating alloy layer of matrix with the metal, and the essentially consist of the Ni-Co-Fe-La-P conductive magneto-conductive glass fibre that we developed sees Table 2; (2) under identical electroless deposition rate conditions, add rare-earth elements La in the plating bath, can make plating temperature reduce by 8 ℃～28 ℃, under the uniform temp condition, add rare-earth elements La and can make the maximum deposition rate of coating improve about 63.46%; (3) surperficial Paint Gloss, the fine and close (see figure 1) of Yan Zhi Ni-Co-Fe-La-P quinary alloy glass fibre, and the electricity, (seeing Fig. 2, table 3 and table 4) has excellent magnetic characteristics.

The composition of table 2 glass fibre Ni-Co-Fe-La-P alloy layer

Fig. 1 (a) and (b) be respectively and under a certain electroplate liquid formulation, do not add and add La ₂O ₃The surface topography graph of a relation of alloy layer.As can be seen, fiberglass surfacing has formed complete alloy layer, and adds La in the plating bath ₂O ₃Back gained coating is more even, smooth and fine and close.

In forming, the above-mentioned electroplate liquid formulation of Electroless Plating Ni-Fe-Co-La-P keeps changing La under the constant condition of other component ₂O ₃Concentration is studied the resistivity of obtained Ni-Fe-Co-La-P alloy layer, the result as shown in Figure 2, the visible glass fibre of result of study has good electrical conductivity.

With microwave four attitudes four port reflexometers, the electromagnetic parameter of obtained Ni-Fe-Co-P and Ni-Fe-Co-La-P alloy layer is under these conditions measured, the research rare earth element is to the influence of electroconductive glass fibre electromagnetic parameter, and selected frequency is 9300MHz, and experimental result sees Table 3 and 4.

Table 3 glass fibre Ni-Fe-Co-P alloy layer electromagnetic parameter

Table 4 glass fibre Ni-Fe-Co-La-P alloy layer electromagnetic parameter

By in table 3 and 4 as can be known, the magnetic permeability of Ni-Fe-Co-P and Ni-Fe-Co-La-P alloy layer all is a plural number, illustrate and have certain magnetic, and the magnetic permeability of Ni-Fe-Co-La-P alloy layer and permittivity ratio Ni-Fe-Co-P alloy layer is big, illustrates that rare-earth elements La can improve the electricity of alloy layer, magnetic property.Simultaneously illustrated that also rare-earth elements La can improve the electromagnetic shielding and the microwave wave-sucking performance of electroless plating electroconductive glass fibre.

Claims (2)

1. fiberglass surfacing Electroless Plating Ni-Co-Fe-La-P quinary alloy plating bath is characterized in that the prescription of plating bath is:

Single nickel salt NiSO ₄6H ₂O:1.8～2.60g/100ml,

Rose vitriol CoSO ₄7H ₂O:0.6～1.80g/100ml,

Inferior sodium phosphate NaH ₂PO ₂H ₂O:2.1～3.50g/100ml,

Ferrous sulfate FeSO ₄7H ₂O:0.5～1.70g/100ml,

Lanthanum trioxide La ₂O ₃: 0.02～0.18g/100ml,

Trisodium Citrate Na ₃C ₆H ₅O ₇2H ₂O:3.0～3.50g/100ml,

Oxysuccinic acid C ₄H ₆O ₅: 0.8～1.70g/100ml,

Succinic Acid C ₄H ₆O ₄: 0.6～1.50g/100ml,

Ammonium sulfate (NH ₄) ₂SO ₄: 3.8～5.0g/100ml,

Distilled water H ₂O:100ml,

Thiocarbamide CH ₄N ₂S:o.oo8～0.05g/100ml,

Urea CO (NH ₂) ₂: 0.9～2.10g/100ml,

Concentrated hydrochloric acid: 2.5～5.50g/100ml.

2. method for preparing the described plating bath of claim 1, it is characterized in that: the preparation process of described Ni-Fe-Co-La-P alloy electroplating bath is as follows:

Step 1, main salt single nickel salt, rose vitriol and ferrous sulfate are put into beaker A, add the distilled water of 95ml;

Step 2, the lanthanum sesquioxide that takes by weighing is put into the B beaker, adds 5ml distilled water and concentrated hydrochloric acid, under the normal temperature in magnetic stirring apparatus stirring and dissolving, join after the dissolving in the A beaker;

Step 3, Trisodium Citrate, oxysuccinic acid, Succinic Acid, ammonium sulfate, inferior sodium phosphate, thiocarbamide and urea add among the beaker A successively, are stirred to fully dissolving, splash into ammoniacal liquor and regulate pH=8.0 ± 0.2, are made into chemical plating fluid.

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