阅读说明：本技术 一种珍珠镍起砂剂组合物和珍珠镍电镀工艺 (Pearl nickel sanding agent composition and pearl nickel electroplating process ) 是由 李日华 于 2020-11-16 设计创作，主要内容包括：本发明属于电镀领域,公开了一种珍珠镍起沙剂组合物,包括主砂剂和辅砂剂,所述主砂剂为苯扎氯铵；所述辅砂剂为具有一对脂肪族长链基团的季铵盐；所述主砂剂和辅砂剂的重量比例为7-9:1-3；所述脂肪族长链的链长为12-16个碳原子；该组合物应用于电镀液中时,能促进电镀液快速起砂、砂面细腻、砂面白,同时,本案还公开了一种珍珠镍电镀工艺。(The invention belongs to the field of electroplating, and discloses a pearl nickel sanding agent composition which comprises a main sanding agent and an auxiliary sanding agent, wherein the main sanding agent is benzalkonium chloride; the auxiliary sand agent is quaternary ammonium salt with a pair of aliphatic long-chain groups; the weight ratio of the main sand agent to the auxiliary sand agent is 7-9: 1-3; the chain length of the long aliphatic chain is 12-16 carbon atoms; when the composition is applied to electroplating solution, the rapid sanding, fine and smooth sand surface and white sand surface of the electroplating solution can be promoted, and meanwhile, the scheme also discloses a pearl nickel electroplating process.)

1. The pearl nickel sanding agent composition is characterized by comprising a main sanding agent and an auxiliary sanding agent, wherein the main sanding agent is benzalkonium chloride; the auxiliary sand agent is quaternary ammonium salt with a pair of aliphatic long-chain groups; the weight ratio of the main sand agent to the auxiliary sand agent is 7-9: 1-3; the chain length of the long aliphatic chain is 12-16 carbon atoms.

2. The pearl nickel sanding agent composition according to claim 1, wherein the two long aliphatic chains in the auxiliary sanding agent have equal chain length.

3. The pearl nickel sanding agent composition according to claim 2, wherein the auxiliary sanding agent is didodecyldimethylammonium chloride, ditetradecyldimethylammonium chloride, or dicetyldimethylammonium chloride.

4. The pearl nickel blasting agent composition according to claim 1, wherein the weight ratio of the main blasting agent to the auxiliary blasting agent is 7.5-8.5: 1.5-2.5.

5. The pearl nickel electroplating process is characterized by comprising the following steps:

step 1: adding pure water into the plating cylinder, and heating to 55-60 ℃;

step 2: sequentially adding boric acid, nickel sulfate and nickel chloride into the solution obtained in the step 1, and stirring, dispersing and dissolving;

and step 3: adding activated carbon powder, stirring, standing, filtering and supplementing pure water;

and 4, step 4: adjusting the pH value of the system to 4.0-4.5;

and 5: adding a jar opener, the pearl nickel blasting agent composition according to any one of claims 1 to 4 to step 4;

the cylinder opener is compounded by saccharin sodium, 2-propylene-1-sodium sulfonate and disodium nonylphenol polyoxyethylene ether succinate sulfonate;

in the steps 1-5, the boric acid is 35-45g/L, the nickel sulfate is 380-480g/L, and the nickel chloride is 35-45 g/L; 1-3g/L of activated carbon powder; 3-5g/L of saccharin sodium; 0.2-0.4g/L of 2-propylene-1-sodium sulfonate and 2-4g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the dosage of the pearl nickel sanding agent composition is 0.2-0.6 ml/L.

6. Pearl nickel electroplating process according to claim 5, characterized in that the cathodic current density is 1-6A/dm²(ii) a The current density of the anode is 1-3A/dm²(ii) a The electroplating time is 3-10 min.

7. The pearl nickel electroplating process according to claim 5, wherein the electroplating time is less than 4min when the amount of the nickel sulfate is 440-450g/L and the weight ratio of the main sand agent to the auxiliary sand agent is 8: 2.

8. The pearl nickel electroplating process according to any one of claims 5 to 7, wherein the anode is a pure nickel plate and the cathode is a copper sheet.

Technical Field

The invention relates to the field of electroplating, in particular to a pearl nickel sanding agent composition and a pearl nickel electroplating process.

Background

Pearl nickel is also called sand city nickel, satin nickel, fog nickel, water fog nickel, sand fog nickel, satin nickel and the like. The plating layer is in a milky white, matt, silk-like, dazzling-free, bright and dazzling mirror-like, soft and comfortable, and semi-hazy extinction state. Various plating layers such as chromium, gold, imitation gold, silver, gun color and the like can be electroplated on the pearl nickel to form sand chromium, sand gold, sand yellow, sand silver and sand ash, so that the decorative effect is more beautiful.

The first method to obtain pearl nickel is a composite plating technique, i.e. adding a dispersed phase (solid particles) formed by a metal compound into a nickel plating solution, suspending the dispersed phase in the plating solution, and co-depositing with nickel ions to form an uneven plating layer, i.e. the traditional pearl nickel. One new theory is that one or two nonionic surfactants are added into a sulfate nickel plating solution, and the surfactant consists of three groups, namely a water increasing base carbon chain or base ring (R bond for short), hydrophilic ether bond (one O I) and polyoxyethylene bond (CH2CH2O), and has the common characteristics that: these substances have an abnormal insolubilizing property, their solubility is rather reduced with the increase of temperature, when the temperature of the solution is increased, the ether bond is unhooked and separated out to make the solution turbid, and the critical temperature value when the solution becomes turbid is called cloud point. Small liquid beads are formed after precipitation, when the diameters of the small liquid beads are 5-30 mm, the small liquid beads are in a power-on state, nickel ions are discharged and deposited, and no nickel is deposited on the adsorbed small liquid beads; after the liquid beads are desorbed, tiny pits can be formed on the original adsorption points, and the steps are repeated to form the uneven pearl nickel layer.

Application number 201811268826.0 discloses a pearl nickel electroplating process, which comprises the following steps: step 1: adding pure water into the plating cylinder, and heating to 55-60 ℃; step 2: sequentially adding boric acid, nickel sulfate and nickel chloride into the solution obtained in the step 1, and stirring, dispersing and dissolving; and step 3: adding activated carbon powder, stirring, standing, filtering and supplementing pure water; and 4, step 4: adjusting the pH value of the system to 4.1-4.5; and 5: adding a jar opening agent and a main sand agent into the step 4; the cylinder opener is compounded by saccharin sodium, 2-propylene-1-sodium sulfonate and disodium nonylphenol polyoxyethylene ether succinate sulfonate; the main sand agent is benzalkonium chloride. It has the advantages of high coating hardness and good pearl effect.

The more demanding customers put forward higher demands on the pearl effect, and the requirements are that no light spot exists, no blue light exists, no oil light exists, and the sand surface is fine. For this requirement, the above-mentioned solutions are not fully satisfactory for the time being.

The scheme needs to further perfect the prior art and obtain a product with whiter sand surface and stronger sand feeling.

Disclosure of Invention

The invention aims to provide a pearl nickel sanding agent composition which can promote quick sanding, fine and white sand surface of electroplating solution when applied to the electroplating solution, and also discloses a pearl nickel electroplating process.

The specific scheme of the invention is as follows: a pearl nickel sanding agent composition comprises a main sanding agent and an auxiliary sanding agent, wherein the main sanding agent is benzalkonium chloride; the auxiliary sand agent is quaternary ammonium salt with a pair of aliphatic long-chain groups; the weight ratio of the main sand agent to the auxiliary sand agent is 7-9: 1-3; the chain length of the long aliphatic chain is 12-16 carbon atoms.

In the pearl nickel sanding agent composition, the chain lengths of the two long aliphatic chains in the auxiliary sanding agent are equal.

In the pearl nickel sanding agent composition, the auxiliary sanding agent is didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium chloride or dihexadecyl dimethyl ammonium chloride.

In the pearl nickel sanding agent composition, the weight ratio of the main sanding agent to the auxiliary sanding agent is 7.5-8.5: 1.5-2.5.

Meanwhile, the invention also discloses a pearl nickel electroplating process, which comprises the following steps:

step 1: adding pure water into the plating cylinder, and heating to 55-60 ℃;

step 2: sequentially adding boric acid, nickel sulfate and nickel chloride into the solution obtained in the step 1, and stirring, dispersing and dissolving;

and step 3: adding activated carbon powder, stirring, standing, filtering and supplementing pure water;

and 4, step 4: adjusting the pH value of the system to 4.0-4.5;

and 5: adding a jar opener, the pearl nickel blasting agent composition according to any one of claims 1 to 4 to step 4;

the cylinder opener is compounded by saccharin sodium, 2-propylene-1-sodium sulfonate and disodium nonylphenol polyoxyethylene ether succinate sulfonate;

in the steps 1-5, the boric acid is 35-45g/L, the nickel sulfate is 380-480g/L, and the nickel chloride is 35-45 g/L; 1-3g/L of activated carbon powder; 3-5g/L of saccharin sodium; 0.2-0.4g/L of 2-propylene-1-sodium sulfonate and 2-4g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the dosage of the pearl nickel sanding agent composition is 0.2-1.0 ml/L.

In the pearl nickel electroplating process, the cathode current density is 4-5A/dm 2; the anode current density is 1-3A/dm 2; the electroplating time is 3-6 min.

In the pearl nickel electroplating process, when the dosage of the nickel sulfate is 380-480g/L and the weight ratio of the main sand agent to the auxiliary sand agent is 8:2, the electroplating time is less than 4 min.

In the pearl nickel electroplating process, the anode is a pure nickel plate, and the cathode is a copper sheet.

The invention has the beneficial effects that:

according to the invention, the relation between the auxiliary sand agent and the main sand agent is researched, the cationic surfactant has the characteristic of compounding, and compared with benzalkonium chloride, the double-long-chain quaternary ammonium salt has better compounding performance, but no matter benzalkonium chloride is used alone or the double-long-chain quaternary ammonium salt is used alone, light spots and a weak sand feeling exist, particularly, the system stability of the single-long-chain quaternary ammonium salt is poor, and the generated product basically has no qualified product. When a small amount of auxiliary sand agent and main sand agent are compounded, the sand feeling is fine and smooth, the sand surface is white, the sand forming is rapid, and the electroplating time is shortened.

Drawings

FIG. 1 is a graph showing the effect of joining between a plating layer and a material in comparative example 1;

FIG. 2 is a view showing the effect of the connection between the plating layer and the material in example 1;

FIG. 3 is a graph showing the effect of the plating layer of comparative example 1;

FIG. 4 is a graph showing the effect of the plating layer of example 1;

FIG. 5 is an effect diagram of the integral plated member of comparative example 1;

FIG. 6 is an effect diagram of the integral plated member of example 1.

Detailed Description

The invention will now be further described with reference to the following examples, which are not to be construed as limiting the invention in any way, and any limited number of modifications which can be made within the scope of the claims of the invention are still within the scope of the claims of the invention.

Example 1:

a pearl nickel electroplating process comprises the following steps:

step 1: adding pure water into the plating cylinder, and heating to 55-60 ℃;

it should be noted that: the method also comprises the steps of chemical nickel plating, copper preplating, copper plating, acid activation and semi-bright nickel plating before the step 1. The above steps are those commonly used in the art and are not described herein in any greater detail.

Step 2: sequentially adding boric acid, nickel sulfate and nickel chloride into the solution obtained in the step 1, and stirring, dispersing and dissolving;

and step 3: adding activated carbon powder, stirring, standing, filtering and supplementing pure water;

and 4, step 4: adjusting the pH value of the system to 4.0-4.5;

and 5: adding a cylinder opening agent and pearl nickel sanding agent composition into the step 4; the pearl nickel sanding agent composition is diluted by 20 times of pure water before being added into a plating tank;

the cylinder opener is compounded by saccharin sodium, 2-propylene-1-sodium sulfonate and disodium nonylphenol polyoxyethylene ether succinate sulfonate;

in the pearl nickel sanding agent composition, benzalkonium chloride is used as a main sanding agent, didodecyldimethylammonium chloride is used as an auxiliary sanding agent, and the weight ratio of the main sanding agent to the auxiliary sanding agent is 8: 2;

wherein, the boric acid is 40g/L, the nickel sulfate is 450g/L, and the nickel chloride is 40 g/L; the active carbon powder is 3 g/L; 5g/L of saccharin sodium; 0.4g/L of 2-propylene-1-sodium sulfonate and 2g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the pearl nickel sanding agent composition is 0.6 ml/L.

In the electroplating process, the anode is a pure nickel plate, and the cathode is a red copper sheet; the cathode current density is 5A/dm 2; the anode current density is 3A/dm²(ii) a The electroplating time is 3.5 min.

Example 2

A pearl nickel electroplating process comprises the following steps:

step 1: adding pure water into the plating cylinder, and heating to 55-60 ℃;

step 2: sequentially adding boric acid, nickel sulfate and nickel chloride into the solution obtained in the step 1, and stirring, dispersing and dissolving;

and step 3: adding activated carbon powder, stirring, standing, filtering and supplementing pure water;

and 4, step 4: adjusting the pH value of the system to 4.1-4.5;

and 5: adding a cylinder opening agent and pearl nickel sanding agent composition into the step 4; the pearl nickel sanding agent composition is diluted by 10 times of pure water before being added into a plating tank;

the cylinder opener is compounded by saccharin sodium, 2-propylene-1-sodium sulfonate and disodium nonylphenol polyoxyethylene ether succinate sulfonate; in the pearl nickel sanding agent composition, benzalkonium chloride is used as a main sanding agent, didodecyldimethylammonium chloride is used as an auxiliary sanding agent, and the weight ratio of the main sanding agent to the auxiliary sanding agent is 8: 2;

wherein, the boric acid is 40g, the nickel sulfate is 450g, and the nickel chloride is 40 g; the active carbon powder is 3 g/L; 4g/L of saccharin sodium; 0.2-0.4g/L of 2-propylene-1-sodium sulfonate; 4g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the pearl nickel sanding agent composition is 0.6 ml/L.

In the electroplating process, the anode is a pure nickel plate, and the cathode is a red copper sheet; the cathode current density is 5A/dm²(ii) a The anode current density is 3A/dm²(ii) a The electroplating time is 4 min.

Example 3

The difference from example 1 is that:

the boric acid is 40g/L, the nickel sulfate is 430g/L, and the nickel chloride is 40 g/L; the active carbon powder is 4 g/L; 4g/L of saccharin sodium; 0.3g/L of 2-propylene-1-sodium sulfonate and 3g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the main sand agent is 0.6 ml/L.

In the pearl nickel sanding agent composition, benzalkonium chloride is used as a main sanding agent, didodecyldimethylammonium chloride is used as an auxiliary sanding agent, and the weight ratio of the main sanding agent to the auxiliary sanding agent is 7: 3;

in the electroplating process, the anode is a pure nickel plate, and the cathode is a red copper sheet; the cathode current density is 5A/dm²(ii) a The anode current density is 3A/dm²(ii) a Electroplating time is 5 min.

Example 4

The difference from example 1 is that:

the boric acid is 38g/L, the nickel sulfate is 450g/L, and the nickel chloride is 38 g/L; 5g/L of activated carbon powder; 4.5g/L of saccharin sodium; 0.2g/L of 2-propylene-1-sodium sulfonate; 2g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the pearl nickel sanding agent composition is 0.6 ml/L.

In the pearl nickel sanding agent composition, benzalkonium chloride is used as a main sanding agent, didodecyldimethylammonium chloride is used as an auxiliary sanding agent, and the weight ratio of the main sanding agent to the auxiliary sanding agent is 9: 1;

in the electroplating process, the anode is a pure nickel plate, and the cathode is a red copper sheet; the cathode current density is 4A/dm²(ii) a The anode current density is 2A/dm²(ii) a Electroplating time is 5 min.

Example 5

The difference from example 1 is that:

the auxiliary sand agent is ditetradecyl dimethyl ammonium chloride; the electroplating time is 6 min.

Example 6

The difference from example 1 is that:

the auxiliary sand agent is dicetyl dimethyl ammonium chloride; the electroplating time is 6 min.

Comparative example 1

A pearl nickel electroplating process comprises the following steps:

step 1: adding pure water into the plating cylinder, and heating to 55-60 ℃;

it should be noted that: the method also comprises the steps of chemical nickel plating, nickel preplating, copper plating, acid activation and semi-bright nickel plating before the step 1. The above steps are those commonly used in the art and are not described herein in any greater detail.

Step 2: sequentially adding boric acid, nickel sulfate and nickel chloride into the solution obtained in the step 1, and stirring, dispersing and dissolving;

and step 3: adding activated carbon powder, stirring, standing, filtering and supplementing pure water;

and 4, step 4: adjusting the pH value of the system to 4.0-4.5;

and 5: adding a cylinder opening agent and a main sand agent composition into the step 4; the main sand agent is diluted by 10 times of pure water before being added into a plating tank;

the cylinder opener is compounded by saccharin sodium, 2-propylene-1-sodium sulfonate and disodium nonylphenol polyoxyethylene ether succinate sulfonate;

the main sand agent is benzalkonium chloride;

wherein, the boric acid is 40g/L, the nickel sulfate is 450g/L, and the nickel chloride is 340 g/L; the active carbon powder is 3 g/L; 5g/L of saccharin sodium; 0.4g/L of 2-propylene-1-sodium sulfonate and 2g/L of disodium nonylphenol polyoxyethylene ether succinate sulfonate; the main sand agent is 0.6 ml/L.

In the electroplating process, the anode is a pure nickel plate, and the cathode is a red copper sheet; the cathode current density is 5A/dm 2; the anode current density is 3A/dm²(ii) a The electroplating time is 7 min.

Performance testing

The method of example 1 was applied to the radiator grille plating trim, with the following test criteria:

1. coating thickness: GB/T4955-2005

2. Electrochemical potential difference of nickel: astm b 764-2009;

3. and (3) micropore test: ASTMB604-1997

4. Coating bonding strength: Q/JLYJ 7110039C-2017.

And (3) detection results:

the thickness of the pearl nickel is 1.50 mm plus or minus 0.03 mm;

electrochemical potential difference of nickel: the potential difference between the pearl nickel layer and the semi-bright nickel layer is 158mv, and the potential difference between the pearl nickel layer and the microporous nickel layer is 42 mv;

the results of the microwell tests for examples 1-6 are:

example 1: 18239pore/cm²(ii) a Example 2: 19573pore/cm²(ii) a Example 3: 17658pore/cm²(ii) a Example 4: 19114pore/cm²(ii) a Example 5: 20836pore/cm²(ii) a Example 6: 20949pore/cm² _.

The test result of the bonding strength of the plating layer is as follows: the coating and the material are not stripped and the coating is not dropped.

FIG. 1 is a graph showing the effect of connection between a plating layer and a material in comparative example 1, and FIG. 2 is a graph showing the effect of connection between a plating layer and a material in example 1;

fig. 3 is a graph showing the effect of the plating layer of comparative example 1, and fig. 4 is a graph showing the effect of the plating layer of example 1.

Fig. 5 is an effect diagram of the integral plated member of comparative example 1, and fig. 6 is an effect diagram of the integral plated member of example 1.

As can be seen from fig. 1 and 2, the combination strength between the two and the material is good.

As can be seen from fig. 3 and 4, the surface of the plated layer is not peeled off.

As can be seen from fig. 5 and 6, the sand surface of example 1 was whiter and the feeling of sand was stronger.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.