CN101457353A - Chemical depositing Ni-P-nano titanic oxide photocatalysis composite coating plating solution and plating method thereof - Google Patents
Chemical depositing Ni-P-nano titanic oxide photocatalysis composite coating plating solution and plating method thereof Download PDFInfo
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- CN101457353A CN101457353A CNA2009101160045A CN200910116004A CN101457353A CN 101457353 A CN101457353 A CN 101457353A CN A2009101160045 A CNA2009101160045 A CN A2009101160045A CN 200910116004 A CN200910116004 A CN 200910116004A CN 101457353 A CN101457353 A CN 101457353A
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Abstract
The invention relates to a chemical Ni-P-nano-TiO2 depositing photo-catalysis composite coating plating solution and a plating method thereof, aiming at solving the problems that the nano-TiO2 photo-catalyst is easy to be deactivated and agglomerate and is difficult to be recovered, and the like. The nano-TiO2 photo-catalytic composite coating plating solution comprises the chemical raw materials as follows: nickel sulfate, sodium hypophosphite, lactic acid, propionic acid, boric acid, nano-TiO2, lead acetate and sodium dodecyl benzene sulfonate. The process conditions for plating a workpiece are defined as follows: the pH value of the composite coating solution is 4.0-5.5; the plating time is 2 hours at the temperature of 75-90 DEG C. On the basis of the particularity of the nano-particle, the prepared composite coating has the functions of anti-corrosion, anti-abrasion, photo-catalysis, self-degradation and recycling. The nano-TiO2 is introduced in chemical plating solution to co-deposit with Ni-P substrate so as to prepare the Ni-P-nano TiO2 chemical composite coating and provide a feasible loading method for the practical application of the nano-TiO2.
Description
Technical field
The present invention relates to a kind of surface chemistry nickel deposited-phosphorus-titanium dioxide (Ni-P-TiO
2) preparation method of composite coating, specifically have the nickel-phosphorus-titanium dioxide Ni-P-TiO of good wear-resisting, corrosion-resistant and photocatalysis performance by chemical plating method preparation
2Functional coating.
Background technology
Nano titanium oxide TiO
2Under the irradiation of light,, promote the degraded of synthesizing or make compound of compound by luminous energy is converted into chemical energy.Nano titanium oxide TiO
2The photocatalyst material photocatalytic degradation is a kind of process of deep oxidation efficiently, and its advantage is: photoetch does not take place after the illumination, and resistance to acids and bases is good, high temperature high voltage resistant, and chemical property is stable, to biological nontoxic; The source is abundant, and energy gap is bigger, produces the electromotive force current potential height in light induced electron and hole, and very strong oxidisability and reductibility are arranged, and shows wide application prospect in fields such as organic synthesis, photodissociation water, environmental improvements.Yet at nano titanium oxide TiO
2Actual use in, be to adopt suspension system, nano titanium oxide TiO mostly
2Fine catalyst exists easy inactivation, easily reunites and reclaims shortcomings such as difficulty, and this also is nano titanium oxide TiO
2Can not realize the major reason of industrialization in the photocatalysis degradation organic contaminant field.
Chemically composited deposition is the inert solid particle that has property by adding in chemical sinking effusion, make it and the matrix metal codeposition, thereby preparation has the complex function coating of property.With fastest developing speed with nickel-phosphorus (Ni-P) alloy as the matrix metal of compound coating.Along with composite study is developed, increasing metal and alloy can be used as the matrix of compound coating, and the insoluble particle that is used for composite deposition has also been expanded greatly.People are by adding different particle (Al in chemical sinking effusion
2O
3, SiC, CaF
2, graphite, PTFE etc.) obtain to have functional compound coatings such as corrosion-resistant, wear-resistant, self-lubricating, high rigidity.
Summary of the invention
In order to solve nano titanium oxide TiO
2The easy inactivation that photocatalyst exists, easily reunite and reclaim problem such as difficulty, the invention provides a kind of chemical deposited nickel-phosphorus-nano titanium dioxide photocatalysis composite coating plating solution and solution and coating method thereof.
Chemical deposited nickel-phosphorus-nano titanium dioxide photocatalysis composite coating plating solution comprises the chemical feedstocks of following proportioning:
Single nickel salt 15～30g/L, inferior sodium phosphate 24g/L, lactic acid 30mL/L, propionic acid 3g/L, boric acid 4.5g/L, nano titanium oxide 2～8g/L, lead acetate 2mg/L, Sodium dodecylbenzene sulfonate 50～200mg/L;
Above-mentioned chemical feedstocks is dissolved in the 1L distilled water, mixes and get final product.
The solution and coating method of chemical deposited nickel-phosphorus-nano titanium dioxide photocatalysis composite coating plating solution comprises following operation steps:
A. prepare nickel-phosphorus (Ni-P) alloy electroplating bath
By above-mentioned prescription, except that titanium dioxide and lead acetate, get other chemical feedstocks and be dissolved in the 820-900mL distilled water,, prepare chemical deposited nickel-phosphorus (Ni-P) alloy electroplating bath;
B. add titanium dioxide nanoparticle
Adding 100mL distilled water, lead acetate are hybridly prepared into suspension liquid in nano titanium oxide, behind the ultra-sonic oscillation 0.5h, add in chemical deposited nickel-phosphorus (Ni-P) alloy electroplating bath, get composite coating plating solution;
C. at workpiece surface plating composite coating plating solution
Adjust composite coating plating solution pH value 4.0～5.5, in 75～90 ℃ of conditions of temperature, plating time 2h, the gained coated substrate is: nickel-phosphorus (Ni-P) alloying constituent is phosphorus % ≈ 3～11wt%, and surplus is a nickel, nano titanium oxide compounding quantity ≈ 4.70～11.32wt%.
The granularity of described nano titanium oxide is 5～20nm; In the phase structure, Detitanium-ore-type accounts for〉90%, surplus is rutile-type and non-crystalline state.
The present invention adopts chemically composited deposition technique, adds titanium dioxide TiO in the chemical plating fluid of nickel-phosphorus (Ni-P) alloy
2Nanoparticle makes it in the matrix metal synsedimentary, can obtain nano titanium oxide TiO
2Chemical composite plating.Based on the singularity of nanoparticle, the composite deposite that makes can present a lot of particular performances.With nano titanium oxide TiO
2Introduce chemical plating fluid and nickel-phosphorus Ni-P matrix codeposition, preparation nickel-phosphorus Ni-P/ nano titanium oxide TiO
2Chemical composite plating is nano titanium oxide TiO
2Practice provides a kind of practicable carrying method.
Useful technique effect of the present invention is embodied in following several aspect:
1, Ni-P-nano-TiO of the present invention
2Chemical sinking effusion adds the high difficult decomposition of the more existing nanochemistry composite deposition of stablizer lead acetate liquid stability.
2, the present invention adds nano titanium oxide TiO in nickel-phosphorus (Ni-P) chemical sinking effusion
2Thereby, realized nano titanium oxide TiO
2Useful load, compare nano titanium oxide TiO with existing nanochemistry compound coating
2The chemical composite plating chemically composited coating photocatalysis performance that superposeed, the degradation rate of UV-irradiation 5h tropeolin-D can reach 70.29%, with nano titanium oxide TiO
2The photocatalysis performance of powder is roughly close.
3, the present invention is directed to the Ni-P-nano-TiO
2Chemically composited coating adds anionic surfactant sodium dodecylbenzene sulfonate respectively in chemical sinking effusion, overcome nano titanium oxide TiO
2Agglomeration in plating bath makes nano titanium oxide TiO
2Homodisperse in coating, Ni-P-TiO
2Nano titanium oxide TiO in the photocatalysis composite coating
2The compounding quantity existing nano chemical composite plating layer of the same type compounding quantity that all is improved largely of comparing can reach 11.32wt%.
4, the nano titanium oxide TiO of the present invention's preparation
2Compare nickel-phosphorus (Ni-P) chemical plating of basic plating bath preparation of chemical composite plating, its hardness, wear-resisting and corrosion resistance nature are greatly improved, and also have photochemical catalysis, the function of degraded certainly, thereby guarantee nano titanium oxide TiO
2Chemical composite plating has more actual application value in the photocatalytic applications field.
5, the photocatalysis coating of the present invention preparation can be applied in that the urban domestic wastewater is handled and trade effluent in the organic degraded, well solved conventional titanium dioxide TiO
2The problem of the difficult recycling of photocatalyst.
Specific embodiments
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
(30 * 20 * 3mm) go up preparation nickel-phosphorus Ni-P/ nano titanium oxide TiO No. 45 steel matrix
2Chemical composite plating.
Chemical deposited nickel-phosphorus-nano titanium dioxide photocatalysis composite coating plating solution comprises the chemical feedstocks of following proportioning:
Single nickel salt 25g/L
Inferior sodium phosphate 24g/L
Lactic acid 30ml/L
Propionic acid 3g/L
Boric acid 4.5g/L
Lead acetate 2mg/L
Sodium dodecylbenzene sulfonate 100mg/L
Nano titanium oxide TiO
28g/L,
Distilled water 1L.
Adopt the plating technic of above-mentioned composite coating plating solution to comprise following operation steps:
A. prepare nickel-phosphorus (Ni-P) alloy electroplating bath
By above-mentioned prescription, except that titanium dioxide and lead acetate, to get other chemical feedstocks and be dissolved in the 900mL distilled water, preparation obtains chemical deposited nickel-phosphorus (Ni-P) alloy electroplating bath;
B. add titanium dioxide nanoparticle
Adding 100mL distilled water, lead acetate are hybridly prepared into suspension liquid in nano titanium oxide, add to behind the ultra-sonic oscillation 0.5h in chemical deposited nickel-phosphorus (Ni-P) alloy electroplating bath, get composite coating plating solution;
C. at workpiece surface plating composite coating plating solution
Workpiece carries out pre-treatment earlier before electroless plating, preprocessing process mainly comprises: workpiece polishing → washing → electrochemical deoiling → washing → pickling → washing → acidic activated → washing.
In the deposition process, workpiece is hung in the composite coating plating solution, adjust composite coating plating solution pH value 5.0, in excusing from death decentralized water-bath, begin plating, in the plating process, use electric mixer to stir stirring velocity 200r/min simultaneously; In 90 ℃ of conditions of temperature, plating time 2h (makes the compound coating matrix No. 45 steel matrix on 30 * 20 * 3mm) workpiece.
Workpiece cleans repeatedly through 60 ℃ of hot water after the electroless plating, gets final product after the drying.
Nano-TiO in the composite deposite matrix
2Compounding quantity adopts the EDS energy spectrometer to measure; Microhardness is tested on MH-6 type microhardness tester, working load 50g; Wearing test is tested aircraft measurements at end wear, adopt the ring disk-like sample, bull ring is adopted external diameter 24mm, interior No. 45 steel through 16mm, Ra0.3, quenching+temper number 52HRC, load 300N, rotating speed 100r/min, wearing-in period 30min with quality before and after the wearing and tearing of electronic analytical balance weighing coating, estimates abrasion resistance properties by abrasion loss; The photocatalysis performance of composite deposite adopts tropeolin-D as model compound, with 20mg/L is that methyl orange solution is a starting point concentration, measure its absorbancy at the maximum absorption wavelength of 464.8nm tropeolin-D, percent of decolourization with methyl orange solution is weighed photocatalysis performance, for ease of relatively, also measured nano titanium oxide TiO simultaneously
2The photocatalysis performance of powder, nano titanium oxide TiO
2The add-on of powder is 1.0g/L.
The Ni-P/ nano-TiO
2Nano titanium oxide TiO in the chemical composite plating
2Compounding quantity is 11.32wt%, and the nanoparticle compounding quantity improves a lot in the existing nano chemical composite plating layer of the same type.
Microhardness is 542.4Hv before the thermal treatment of nickel-phosphorus (Ni-P) chemical plating, and microhardness is 946.7Hv after 400 ℃ of thermal treatments; Nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2Microhardness is 684.7Hv before the chemical composite plating thermal treatment, and microhardness is 1198.8Hv after 400 ℃ of thermal treatments.
Nickel-phosphorus (Ni-P) chemical plating abrasion loss is 28.7mg, nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2The chemical composite plating abrasion loss is 8.7mg, Ni-P/ nano-TiO in the present embodiment
2The hardness and the wear resisting property of chemical composite plating all are greatly improved.
Nickel-phosphorus (Ni-P) chemical plating does not almost have Degradation to tropeolin-D, nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2The degradation rate of chemical composite plating UV-irradiation 5h tropeolin-D can reach 70.29%, with nano titanium oxide TiO
2The photocatalysis performance of powder is roughly close, but nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2Chemical composite plating is a nano-TiO
2A kind of practicable carrying method is provided.
Embodiment 2:
1, plating bath is formed:
Single nickel salt 15g/L
Inferior sodium phosphate 24g/L
Lactic acid 30ml/L
Propionic acid 3g/L
Boric acid 4.5g/L
Lead acetate 2mg/L
Sodium dodecylbenzene sulfonate 50mg/L
Nano titanium oxide TiO
22g/L
Distilled water 1L.
2, processing condition of the present invention
Stirring velocity 100r/min
75 ℃ of temperature
PH value 4.0
Plating time 2h.
3, checking result:
The Ni-P-nano-TiO
2Nano-TiO in the chemical composite plating
2Compounding quantity is 4.7wt%.
Microhardness is 542.4Hv before the thermal treatment of nickel-phosphorus (Ni-P) chemical plating, and microhardness is 946.7Hv after 400 ℃ of thermal treatments; The Ni-P-nano-TiO
2Microhardness is 606.7Hv before the chemical composite plating thermal treatment, and microhardness is 1018.2Hv after 400 ℃ of thermal treatments.
Nickel-phosphorus (Ni-P) chemical plating abrasion loss is 28.7mg, nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2The chemical composite plating abrasion loss is 9.6mg.
Nickel-phosphorus (Ni-P) chemical plating does not almost have Degradation to tropeolin-D, the Ni-P-nano-TiO
2The degradation rate of chemical composite plating UV-irradiation 5h tropeolin-D can reach 59.39%.
Other is with embodiment 1.
Embodiment 3:
1, plating bath is formed
Single nickel salt 30g/L
Inferior sodium phosphate 24g/L
Lactic acid 30ml/L
Propionic acid 3g/L
Boric acid 4.5g/L
Lead acetate 2mg/L
Sodium dodecylbenzene sulfonate 200mg/L
Nano-TiO
28g/L
Distilled water 1L.
2, processing condition of the present invention
Stirring velocity 300r/min
90 ℃ of temperature
PH value 5.5
Plating time 2h.
3, checking result:
The Ni-P-nano-TiO
2Nano-TiO in the chemical composite plating
2Compounding quantity is 9.32wt%.
Microhardness is 542.4Hv before the thermal treatment of nickel-phosphorus (Ni-P) chemical plating, and microhardness is 946.7Hv after 400 ℃ of thermal treatments; The Ni-P-nano-TiO
2Microhardness is 627.1Hv before the chemical composite plating thermal treatment, and microhardness is 1102.3Hv after 400 ℃ of thermal treatments.
Nickel-phosphorus (Ni-P) chemical plating abrasion loss is 28.7mg, nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2The chemical composite plating abrasion loss is 9.1mg.
Nickel-phosphorus (Ni-P) chemical plating does not almost have Degradation to tropeolin-D, nickel-phosphorus (Ni-P)/nano titanium oxide TiO
2The degradation rate of chemical composite plating UV-irradiation 5h tropeolin-D can reach 63.27%.
Other is with embodiment 1.
Claims (3)
1, chemical deposited nickel-phosphorus-nano titanium dioxide photocatalysis composite coating plating solution is characterized in that: the chemical feedstocks that comprises following proportioning:
Single nickel salt 15～30g/L, inferior sodium phosphate 24g/L, lactic acid 30mL/L, propionic acid 3g/L, boric acid 4.5g/L, nano titanium oxide 2～8g/L, lead acetate 2mg/L, Sodium dodecylbenzene sulfonate 50～200mg/L;
Above-mentioned chemical feedstocks is dissolved in the 1L distilled water, mixes and get final product.
2, the solution and coating method of chemical deposited nickel-phosphorus according to claim 1-nano titanium dioxide photocatalysis composite coating plating solution is characterized in that comprising following operation steps:
A. prepare the nickel-phosphor alloy plating bath
By above-mentioned prescription, except that titanium dioxide and lead acetate, get other chemical feedstocks and be dissolved in the 820-900mL distilled water, prepare chemical deposited nickel-phosphorus alloy plating liquid;
B. add titanium dioxide nanoparticle
Adding 100mL distilled water, lead acetate are hybridly prepared into suspension liquid in nano titanium oxide, behind the ultra-sonic oscillation 0.5h, add in chemical deposited nickel-phosphorus alloy plating liquid, get composite coating plating solution;
C. at workpiece surface plating composite coating plating solution
Adjust composite coating plating solution pH value 4.0～5.5, in 75～90 ℃ of conditions of temperature, plating time 2h, the gained coated substrate is: the nickel-phosphor alloy composition is phosphorus % ≈ 3～11wt%, and surplus is a nickel, nano titanium oxide compounding quantity ≈ 4.70～11.32wt%.
3, chemical deposited nickel-phosphorus according to claim 2-nano titanium dioxide photocatalysis composite coating plating solution is characterized in that: the granularity of described nano titanium oxide is 5～20nm; In the phase structure, Detitanium-ore-type accounts for〉90%, surplus is rutile-type and non-crystalline state.
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| CN103993298A (en) * | 2014-04-29 | 2014-08-20 | 浏阳市三鹰新材料有限责任公司 | Surface repair nano composite plating and process used for reproducing |
| CN104789950A (en) * | 2015-03-18 | 2015-07-22 | 北京科技大学 | Photocatalytic plating preparation method for material surface metal pattern |
| CN107190250A (en) * | 2017-05-24 | 2017-09-22 | 李华平 | The nano chemical composite plating liquid and its application method of a kind of plated state high-hardness, wearable |
| CN108906129A (en) * | 2018-06-22 | 2018-11-30 | 东华大学 | It is a kind of based on composite electroless-plating fiber base nickel-loaded/optically catalytic TiO 2 degradable material preparation method |
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2009
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| CN103993298A (en) * | 2014-04-29 | 2014-08-20 | 浏阳市三鹰新材料有限责任公司 | Surface repair nano composite plating and process used for reproducing |
| CN103993298B (en) * | 2014-04-29 | 2016-05-04 | 浏阳市三鹰新材料有限责任公司 | Nano composite plating layer process is repaired on a kind of surface of manufacturing again that is applied to |
| CN104789950A (en) * | 2015-03-18 | 2015-07-22 | 北京科技大学 | Photocatalytic plating preparation method for material surface metal pattern |
| CN107190250A (en) * | 2017-05-24 | 2017-09-22 | 李华平 | The nano chemical composite plating liquid and its application method of a kind of plated state high-hardness, wearable |
| CN108906129A (en) * | 2018-06-22 | 2018-11-30 | 东华大学 | It is a kind of based on composite electroless-plating fiber base nickel-loaded/optically catalytic TiO 2 degradable material preparation method |
| CN114016008A (en) * | 2021-10-27 | 2022-02-08 | 东北电力大学 | Chemical plating Ni-P-PTFE-TiO2Composite nano-coating and preparation method thereof |
| CN114016008B (en) * | 2021-10-27 | 2023-08-29 | 东北电力大学 | Electroless Ni-P-PTFE-TiO plating 2 Composite nano-coating and preparation method thereof |
| WO2023201394A1 (en) * | 2022-04-22 | 2023-10-26 | Monash University | A method of oxidising an inorganic amine to nitrate |
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