CN105154942A - Method for preparing Ni-P-WO3 nano-composite coating through pulse electrodeposition - Google Patents

Abstract

The invention discloses a method for preparing a Ni-P-WO3 nano-composite coating through pulse electrodeposition. The method for preparing the Ni-P-WO3 nano-composite coating through pulse electrodeposition comprises the steps that firstly, a plating solution is prepared according to requirements; secondly, a carbon steel base body is preprocessed, namely the carbon steel base body is polished through abrasive paper, washed through distilled water, chemically deoiled, washed through distilled water, pickled, activated and washed through distilled water; and finally, plating is conducted. The optimum plating condition is determined with the deposition rate, the microhardness and the surface topography as inspection indexes. According to the method, operation is easy and convenient, control is easy, the plating solution is stable and not prone to going bad, and the prepared Ni-P-WO3 nano-composite coating has excellent performance and has excellent corrosion inhibition performance in simulated sea water; the coating has broad application prospects in the functional composite plating field.

Description

Pulse electrodeposition prepares Ni-P-WO 3the method of nano-composite plate

Technical field

The invention belongs to impulse electrodeposition technology field, particularly a kind of pulse electrodeposition prepares Ni-P-WO ₃the method of nano-composite plate.

Background technology

Metal corrosion and protection technology is the focus of Chinese scholars research always.Environmental friendliness, high-performance and long-effective corrosion technology are also the major objectives of current scientist.Corrosion of metal has surface treatment and coating technology, inhibiter technology, cathode protection technology with protection major technique.Wherein photic cathode protection technology is the novel cathode guard method proposed by Japanese scholars the nineties in 20th century; semiconductor film is coated on protected metal; in protection process, semiconductor film is not sacrificed, and can become permanent protection coating, has the advantage of saving resource.TiO ₂be a kind of stable, nontoxic, inexpensive semiconductor material, as cathodic protection coatings, can produce galvanic protection effect on the one hand under illumination, the existence of coating can avoid impressed current cathodic protection method to need the shortcoming of additional power source on the other hand.But photic cathode protection technology also also exists some technical problems: in the common substrate such as carbon steel, bonding force is insecure; to visible ray utilization ratio low (only absorbing UV-light); under dark-state, the quick compound of photo-generate electron-hole makes its protective efficacy low; these problems are keys that photic cathode protection technology moves towards practical, and this has important theoretical and practical significance for the protection realizing the metallic substance such as carbon steel under natural environmental condition.

In order to solve the problems referred to above that photic galvanic protection exists, scientists is to TiO ₂exploratory development is carried out in modification doping.Find in existing research, at TiO ₂the conductor oxidate with charge storage ability that is coupled in film can make its electronics discharging storage in the dark state and extend galvanic protection efficiency; And at TiO ₂in coating, doping metals or non-metallic element can make its band gap reduce, and increase the utilization ratio of visible ray, but be mostly still in the exploratory stage, a lot of practical problems is not resolved.

Impulse electrodeposition technology is utilized first to prepare Ni-P-WO on plain steel ₃nano-composite plate middle layer, not only can improve TiO ₂the bonding force of coating and matrix, secondly can play WO ₃storage electronic capability, outer TiO can be made ₂coating continues to maintain photic galvanic protection effect in the dark state, and Ni-P coating after heat treatment in addition, and Ni, P can be used as doped element and be doped to TiO ₂in coating, affect TiO ₂energy band structure, improves its utilization ratio to visible ray, for photic galvanic protection is implemented to provide support smoothly.In addition, impulse electrodeposition technology is utilized to prepare Ni-P-WO ₃electroplate liquid formulation and the processing method of nano-composite plate have not been reported.

Summary of the invention

The object of this invention is to provide a kind of pulse electrodeposition and prepare Ni-P-WO ₃the method of nano-composite plate.

Thinking of the present invention: by utilizing impulse electrodeposition technology, by WO ₃nanoparticle and Ni, P codeposition, preparation Ni-P-WO ₃nano-composite plate, can be used as matrix and TiO ₂the middle layer of layer, improves TiO ₂the bonding force of coating and matrix, WO in coating ₃particle can in performance storage electronic capability, and extend the photic galvanic protection time in the dark state, in this serving, Ni, P can be used as doped element and be doped to TiO in thermal treatment ₂in coating, improve its utilization ratio to visible ray.This Ni-P-WO prepared ₃nano-composite plate itself has excellent properties, WO ₃uniform particle is distributed in coating, coating in the sodium chloride solution of 3.5% inhibition efficiency up to more than 90%.

Concrete steps are:

(1) plating solution is prepared

A. by NiSO ₄6H ₂o, NiCl ₂6H ₂o, H ₂bO ₃, NaH ₂pO ₄h ₂o, asccharin, sodium lauryl sulphate are dissolved in distilled water obtain solution respectively, wherein NiSO ₄6H ₂o concentration is 120g/L, NiCl ₂6H ₂o concentration is 40g/L, H ₂bO ₃concentration is 36g/L, NaH ₂pO ₄h ₂o concentration is 20g/L, asccharin concentration is 2g/L, and sodium lauryl sulphate concentration is 0.1g/L, and after volumetric flask constant volume, ageing 8h is stand-by; Agents useful for same is analytical pure.

B. measure step (1) a to walk in the solution injection electrolyzer of preparation, adjust ph, between 4 ~ 4.5, adds the nanometer WO that particle diameter is 95 ~ 105nm ₃particle, in above-mentioned solution, is put into ultrasonic apparatus and is carried out ultrasonic vibration 1h and make nanometer WO ₃uniform particle disperses and particle concentration is 2 ~ 2.5g/L.

(2) pre-treatment plain steel

Plain steel is followed these steps to carry out pre-treatment: sand papering, distillation washing, electrochemical deoiling, distillation washing, acid-wash activation, distillation are washed, weighed.

(3) plating is carried out

Pure Ni plate and step (2) pretreated plain steel being fixed on step (1) b walks in the electrolyzer of use; the plating solution that step (1) is prepared is filled in electrolyzer; wherein pure Ni plate is as anode; step (2) pretreated plain steel is as negative electrode; and connect with wire and the pulse power; electrolyzer is placed in water bath with thermostatic control, ensures in plating process, the bath temperature that step (1) obtains is at 55 ~ 60 DEG C; Arrange pulse parameter, controlling average current density is j _m=2 ~ 2.5A/dm ², dutycycle R is 25 ~ 35%, and pulse-repetition is 100 ~ 150Hz, and the burst length is 30 ~ 40min, carries out plating i.e. obtained Ni-P-WO ₃nano-composite plate.

The inventive method is simple, convenient, be easy to operate and control, bath stability, not perishable, the Ni-P-WO prepared ₃nano-composite plate better performances, has good application prospect.

Embodiment

embodiment:

(1) plating solution is prepared

A. by NiSO ₄6H ₂o, NiCl ₂6H ₂o, H ₂bO ₃, NaH ₂pO ₄h ₂o, asccharin, sodium lauryl sulphate are dissolved in distilled water obtain solution respectively, wherein NiSO ₄6H ₂o concentration is 120g/L, NiCl ₂6H ₂o concentration is 40g/L, H ₂bO ₃concentration is 36g/L, NaH ₂pO ₄h ₂o concentration is 20g/L, asccharin concentration is 2g/L, and sodium lauryl sulphate concentration is 0.1g/L, and after volumetric flask constant volume, ageing 8h is stand-by; Agents useful for same is analytical pure.

B. measure step (1) a to walk in the solution injection electrolyzer of preparation, adjust ph, between 4 ~ 4.5, adds the nanometer WO that particle diameter is 100nm ₃particle, in above-mentioned solution, is put into ultrasonic apparatus and is carried out ultrasonic vibration 1h and make nanometer WO ₃uniform particle disperses and particle concentration is 2g/L.

(2) pre-treatment plain steel

Plain steel is followed these steps to carry out pre-treatment: sand papering, distillation washing, 60 DEG C of alkali liquor oil removing 15min, distillation washing, 5% chlorohydric acid pickling 3min, distillations are washed, weighed.

(3) plating is carried out

Pure Ni plate and step (2) pretreated plain steel being fixed on step (1) b walks in the electrolyzer of use; the plating solution that step (1) is prepared is filled in electrolyzer; wherein pure Ni plate is as anode; step (2) pretreated plain steel is as negative electrode; and connect with wire and the pulse power; electrolyzer is placed in water bath with thermostatic control, ensures in plating process, the bath temperature that step (1) obtains is at 60 DEG C; Arrange pulse parameter, controlling average current density is j _m=2A/dm ², dutycycle R is 30%, and pulse-repetition is 150Hz, and the burst length is 35min, carries out plating i.e. obtained Ni-P-WO ₃nano-composite plate.

The Ni-P-WO that the present embodiment is obtained ₃plated layer compact is complete, and nano surface particle distribution is even, through X-ray diffractometer test coating phase structure, and WO ₃nanoparticle dispersion is in coating, and under titanizing, coating is amorphous state, crystallization gradually after 200 DEG C, 400 DEG C, 600 DEG C thermal treatment, and microhardness is significantly increased after heat treatment; With with Ni-P-WO ₃the carbon steel base of coating is Electrode, three-electrode system test is carried out in the sodium chloride solution of 3.5%, polarization curve and ac impedance spectroscopy test result show that coating has excellent corrosion mitigating effect, although its inhibition efficiency is not as good as Ni-P coating, also up to more than 90%, and pulse electrodeposition prepares Ni-P-WO ₃coating is combined with matrix firmly, can as matrix and TiO ₂the middle layer of layer, WO in coating ₃particle can play storage electronic capability, and expectation can extend the photic galvanic protection time in the dark state, and Ni, P can be doped to TiO as doped element in thermal treatment ₂in coating, estimate to improve its utilization ratio to visible ray.

Claims (1)

1. a pulse electrodeposition prepares Ni-P-WO ₃the method of nano-composite plate, is characterized in that concrete steps are:

(1) plating solution is prepared

A. by NiSO ₄6H ₂o, NiCl ₂6H ₂o, H ₂bO ₃, NaH ₂pO ₄h ₂o, asccharin, sodium lauryl sulphate are dissolved in distilled water obtain solution respectively, wherein NiSO ₄6H ₂o concentration is 120g/L, NiCl ₂6H ₂o concentration is 40g/L, H ₂bO ₃concentration is 36g/L, NaH ₂pO ₄h ₂o concentration is 20g/L, asccharin concentration is 2g/L, and sodium lauryl sulphate concentration is 0.1g/L, and after volumetric flask constant volume, ageing 8h is stand-by; Agents useful for same is analytical pure;

B. measure step (1) a to walk in the solution injection electrolyzer of preparation, adjust ph, between 4 ~ 4.5, adds the nanometer WO that particle diameter is 95 ~ 105nm ₃particle, in above-mentioned solution, is put into ultrasonic apparatus and is carried out ultrasonic vibration 1h and make nanometer WO ₃uniform particle disperses and particle concentration is 2 ~ 2.5g/L;

(2) pre-treatment plain steel

Plain steel is followed these steps to carry out pre-treatment: sand papering, distillation washing, electrochemical deoiling, distillation washing, acid-wash activation, distillation are washed, weighed;

(3) plating is carried out

Pure Ni plate and step (2) pretreated plain steel being fixed on step (1) b walks in the electrolyzer of use; the plating solution that step (1) is prepared is filled in electrolyzer; wherein pure Ni plate is as anode; step (2) pretreated plain steel is as negative electrode; and connect with wire and the pulse power; electrolyzer is placed in water bath with thermostatic control, ensures in plating process, the bath temperature that step (1) obtains is at 55 ~ 60 DEG C; Arrange pulse parameter, controlling average current density is j _m=2 ~ 2.5A/dm ², dutycycle R is 25 ~ 35%, and pulse-repetition is 100 ~ 150Hz, and the burst length is 30 ~ 40min, carries out plating i.e. obtained Ni-P-WO ₃nano-composite plate.