CN100595326C - Ni-Fe-La-P four-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-Fe-La-P quaternary alloy bath and the preparation method thereof, which is characterized in that the alloy bath consists of nickel sulfate, ferrous sulfate, lanthanum oxide, sodium citrate, malic acid, succinic acid, inferior sodium phosphate, ammonium sulfate, distilled water, thiourea, urea and concentrated hydrochloric acid. The preparation method is as follows: the main salt nickel sulfate and the ferrous sulfate are put in the distilled water; the lanthanum sesquioxide, the distilled water and the concentrated hydrochloric acidare 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 thedistilled 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 1.8 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

Ni-Fe-La-P four-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 Ni-Fe-La-P four-component alloy plating solution for chemical plating on surface of fiberglass and preparation method thereof.

Background technology

At present, more to the report of electroless plating ternary alloy both at home and abroad, quad alloy is less with the report of relevant rare earth element electroless plating, and most ofly carries out plating on metallic matrix, and the research of rare earth element adding glass fibre electroless plating does not appear in the newspapers.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 Ni-Fe-La-P four-component alloy plating solution for chemical plating on surface of fiberglass and preparation method thereof, single nickel salt and ferrous sulfate are 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-Fe-La-P alloy electroplating bath is characterized in that consisting of of alloy electroplating bath:

Single nickel salt NiSO ₄6H ₂O:1.6～2.60g/100ml,

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

Lanthanum trioxide La ₂O ₃: 0.01～0.18g/100ml,

Trisodium Citrate Na ₃C ₆H ₅O ₇2H ₂O:3.0～5.0g/100ml,

Oxysuccinic acid C ₄H ₆O ₅: 0.5～1.60g/100ml,

Succinic Acid C ₄H ₆O ₄: 0.6～1.40g/100ml,

Inferior sodium phosphate NaH ₂PO ₂H ₂O:2.0～3.50g/100ml,

Ammonium sulfate (NH ₄) ₂SO ₄: 3.6～5.50g/100ml,

Distilled water H ₂O:100ml,

Thiocarbamide CH ₄N ₂S:0.008～0.05g/100ml,

Urea CO (NH ₂) ₂): 0.9～2.10g/100ml

Concentrated hydrochloric acid HCl:2.5～5.5g/100ml.

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

Step 1, main salt single nickel salt 1.6～2.60g, ferrous sulfate 0.5～1.70g are put into beaker A, add the distilled water of 95ml;

Step 2, lanthanum sesquioxide 0.01～0.18g is put into beaker B, adds 5ml distilled water and 2.5～5.5g concentrated hydrochloric acid, under the normal temperature in magnetic stirring apparatus stirring and dissolving, the dissolving back adds among the beaker A;

Step 3, Trisodium Citrate 3.0～5.0g, oxysuccinic acid 0.5～1.60g, Succinic Acid 0.6～1.40g, ammonium sulfate 3.6～5.50g, inferior sodium phosphate 2.0～3.50g, thiocarbamide 0.008～0.05g and urea 0.9～2.10g are added among the beaker A successively, be stirred to dissolving fully, splash into ammoniacal liquor and regulate pH=8.0 ± 0.2, be made into chemical plating fluid.

Beneficial effect

The present invention proposes a kind of Ni-Fe-La-P four-component alloy plating solution for chemical plating on surface of fiberglass, 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, Fe in the alloy layer, and in alloy layer, introduced rare-earth elements La, greatly reduce P content, can also reduce the plating temperature of electroless plating simultaneously.In chemical plating fluid, add in the obtained alloy layer of proper amount of rare-earth oxide compound phosphorus content 1.8%～17%, and tradition with the metal be in the electroless plating alloy layer of matrix phosphorus content 15%～32%; Prepared 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 (1.91g), ferrous sulfate (0.82g) are put into 250ml, add the distilled water of 95ml.

Step 2, take by weighing the beaker that lanthanum sesquioxide (0.10g) 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 (3.80g), oxysuccinic acid (1.12g), Succinic Acid (0.85g), inferior sodium phosphate (2.70g), ammonium sulfate (4.0g), thiocarbamide (0.02g) and urea (1.10g) 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 above-mentioned 1 and is filled the beaker that the chemistry that has prepared crosses liquid, and heating in water bath reacts 20～60min down at 50 ℃～70 ℃; The glass fibre that pre-treatment is good is put into the beaker that the chemistry that has prepared crosses 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 ℃.Promptly make glass fibre Electroless Plating Ni-Co-La-P quad alloy coating.

The characteristics of the Electroless Plating Ni-Fe-La-P conductive magneto-conductive glass fibre of the present invention's development are that (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 Ni in the alloy layer, Fe content, reduce P content greatly, in chemical plating fluid, add an amount of La ₂O ₃, phosphorus content is 1.8%～17% in the obtained alloy layer, and tradition is that phosphorus content is 15%～32% in the electroless plating alloy layer of matrix with the metal, and the essentially consist of the Ni-Fe-La-P electroconductive 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 6 ℃～20 ℃, under the uniform temp condition, add rare-earth elements La and can make the maximum deposition rate of coating improve about 23～31%; (3) surperficial Paint Gloss, the fine and close (see figure 1) of Yan Zhi Ni-Fe-La-P quad 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-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-La-P keeps changing La under the constant condition of other component ₂O ₃Concentration is studied the resistivity of obtained Ni-Fe-La-P alloy layer, and the result is illustrated in fig. 2 shown below:

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

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

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

By in table 3 and 4 as can be known, the magnetic permeability of Ni-Fe-P and Ni-Fe-La-P alloy layer all is a plural number, illustrate and have certain magnetic, and the magnetic permeability of Ni-Fe-La-P alloy layer and permittivity ratio Ni-Fe-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. Ni-Fe-La-P four-component alloy plating solution for chemical plating on surface of fiberglass is characterized in that consisting of of alloy electroplating bath:

Single nickel salt NiSO ₄6H ₂O:1.6～2.60g/100ml,

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

Lanthanum trioxide La ₂O ₃: 0.01～0.18g/100ml,

Trisodium Citrate Na ₃C ₆H ₅O ₇2H ₂O:3.0～5.0g/100ml,

Oxysuccinic acid C ₄H ₆O ₅: 0.5～1.60g/100ml,

Succinic Acid C ₄H ₆O ₄: 0.6～1.40g/100ml,

Inferior sodium phosphate NaH ₂PO ₂H ₂O:2.0～3.50g/100ml,

Ammonium sulfate (NH ₄) ₂SO ₄: 3.6～5.50g/100ml,

Distilled water H ₂O:100ml,

Thiocarbamide CH ₄N ₂S:0.008～0.05g/100ml,

Urea CO (NH ₂) ₂: 0.9～2.10g/100ml

Concentrated hydrochloric acid HCl:2.5～5.5g/100ml.

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

Step 1, main salt single nickel salt 1.6～2.60g, ferrous sulfate 0.5～1.70g are put into beaker A, add the distilled water of 95ml;

Step 2, lanthanum sesquioxide 0.01～0.18g is put into beaker B, adds 5ml distilled water and 2.5～5.5g concentrated hydrochloric acid, under the normal temperature in magnetic stirring apparatus stirring and dissolving, the dissolving back adds among the beaker A;

Step 3, Trisodium Citrate 3.0～5.0g, oxysuccinic acid 0.5～1.60g, Succinic Acid 0.6～1.40g, ammonium sulfate 3.6～5.50g, inferior sodium phosphate 2.0～3.50g, thiocarbamide 0.008～0.05g and urea 0.9～2.10g are added among the beaker A successively, be stirred to dissolving fully, splash into ammoniacal liquor and regulate pH=8.0 ± 0.2, be made into chemical plating fluid.

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