CN105692700A - Preparation method and application of tungsten trioxide nanoparticles capable of stably suspending in plating solution with high ion concentration - Google Patents

Preparation method and application of tungsten trioxide nanoparticles capable of stably suspending in plating solution with high ion concentration Download PDF

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Publication number
CN105692700A
CN105692700A CN201610018894.6A CN201610018894A CN105692700A CN 105692700 A CN105692700 A CN 105692700A CN 201610018894 A CN201610018894 A CN 201610018894A CN 105692700 A CN105692700 A CN 105692700A
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preparation
solution
plating solution
concentration
tungsten trioxide
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CN201610018894.6A
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CN105692700B (en
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丹媛媛
陈立庄
于化龙
张丽
孙园园
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Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a preparation method of tungsten trioxide nanoparticles capable of stably suspending in a plating solution with a high ion concentration.The method comprises the steps that sodium tungstate serves as the raw material, hydrochloric acid serves as a precipitating agent, and lauryl sodium sulfate and polyacrylic acid serve as surface modification agents; lauryl sodium sulfate and polypropylene are stirred and mixed to be uniform, a mixed solution is added to a Na2WO4 aqueous solution, and a concentrated hydrochloric acid solution is rapidly added to the system under the stirring condition till yellow precipitate appears; the reaction system is subjected to an ultrasonic stirring reaction at room temperature; after the reaction is completed, nano WO3 is filtered, washed and subjected to vacuum drying.The preparation process is simple, the period is short, and the product is easy to store, excellent in quality and low in price.

Description

Can the preparation method of tungsten trioxide nano particle of stable suspersion and application in high ion concentration plating solution
Technical field
The present invention relates to field of nanometer technology, more particularly to a kind of WO with well suspended3Nanoparticle, more particularly to a kind of WO suitable in composite plating3Nanoparticle。
Background technology
Nineteen twenty-eight (FinkCG is traced back in composite plating application the earliest, PrinceJD.Codepositionofcopperandgraphite [J] .Trans.Am.Electrochem.Soc., 1928,54:315-321), this method is for preparing the copper-graphite electrode composite deposite on car engine。From twentieth century beginning of the fifties the to the end of the sixties, research about this respect increases (WilliamsRV.ElectrodepositedCompositeCoatings [J] .ElectroplatingandMetalFinishing gradually, 1966,19 (3): 92-96.)。During twentieth century this section seventies to eighties, the focus of research is concentrated mainly on the mechanical strength of strengthening membrane, anticorrosion, wear-resisting character。Until at twentieth century beginning of the nineties, Kunugi et al. takes the lead in adopting composite plating to prepare Ni+PTFE, and use it for electrocatalytic oxidation Organic substance (KunugiY, FuchigamiT, NonakaT, MatsumuraS.Electrolysisusingcomposite-platedelectrodes:P artII.Electrooxidationofalcoholsatahydrophobicnickel/pol y (tetrafluoroethylene) composite-platedanode [J] .JournalofElectroanalyticalChemistryandInterfacialElectr ochemistry, 1990, 287:385-388；KunugiY, KumadaR, NonakaT, ChongTB, WatanabeN.Electrolysisusingcomposite-platedelectrodes:Pa rtIII.ElectroorganicreactionsonahydrophobicNi/PTFEcompos ite-platednickelelectrode [J] .JournalofElectroanalyticalChemistryandInterfacialElectr ochemistry, 1991,313:215-225]。Hereafter, the research worker such as MusianiM, Kawai, Yoneyama have carried out a series of research successively, this method is utilized to prepare composite functional material (MusianiM.ElectrodepositionofComposites:AnExpandingSubjec tinElectrochemicalMaterialsScience [J] .ElectrochimicaActa such as multiple catalysis, photosensitive, energy storage, 2000,45 (20): 3397-3402；MusianiM, FurlanettoF, BertoncelloR.ElectrodepositedPbO2+RuO2: acompositeanodeforoxygenevolutionfromsulphuricacidsoluti on [J] .JournalofElectroanalyticalChemistry, 1999,465:160-167；KawaiK, MiharaN, KuwabataS, YoneyamaH.ElectrochemicalSynthesisofPolypyrroleFilmsCont ainingTiO2PowderParticles [J] .JournalofElectrochemistrySociety, 1990,137:1793-1796；YoneyamaH, KishimotoA, KuwabataS.Charge-dischargepropertiesofpolypyrrolefilmsco ntainingmanganesedioxideparticles [J] .JournaloftheChemicalSociety, ChemicalCommunications, 1991,15:986-987；KuwabataS, KishimotoA, TanakaT, YoneyamaH.ElectrochemicalSynthesisofCompositeFilmsofMang aneseDioxideandPolypyrroleandTheirPropertiesasanActiveMa terialinLithiumSecondaryBatteries [J] .JournalofElectrochemistrySociety, 1994,141 (1): 10-15)。
Development along with nanotechnology, composite plating combines with nanotechnology, theoretical theoretical with dispersion-strengtherning according to electrocrystallization, pass through electrochemical method, make one or more insoluble nano-solid granules and metal ion at electrode surface generation codeposition, nanoparticle is wrapped in metal oxide matrix, thus obtaining composite function nano material。
Composite plating it is critical only that deposition process all can be brought impact by the doping particle diameter of character particle of particle, density, electric conductivity, wettability and crystalline structure。The particle diameter of particle is more little, and the wettability of particle is more good, be more advantageous in that smoothly with metal/metal oxide codeposition；The particle that conductive capability is strong is more easily embedded in coating。So, preparation is suitable for the key that the nanoparticle of composite plating is this technical field。
Summary of the invention
Goal of the invention: for solving problems of the prior art, the present invention provide a kind of in high ion concentration plating solution can the preparation method of tungsten trioxide nano particle of stable suspersion, by choosing kind and the consumption of coating material, add WO3Nanoparticle dispersibility in the plating solution and suspension。
Technical scheme: for realizing above-mentioned technical purpose, provided by the invention can in high ion concentration plating solution the WO of stable suspersion3The preparation method of nanoparticle comprises the steps:
(1) it is 3～5: 1～2 be mixed and stirred for by mass percentage by 5～15wt% sodium lauryl sulphate and 2～6wt% polyacrylic acid, obtains finishing liquid；
(2) in the water-bath of 95～100 DEG C, described finishing liquid is joined 2～6wt%Na2WO4In aqueous solution and stir, wherein, finishing liquid and Na2WO4Aqueous solution or amount ratio for for 4: 1～3: 1；
(3) under agitation, in the system that step (2) obtains, in system, add 10～30wt% hydrochloric acid solution with the 1s/ speed dripped, occur to yellow mercury oxide；
(4) reaction system that step (3) obtains at room temperature is cooled down, ultrasonic agitation；
(5) yellow product filtered, wash, after vacuum drying, obtain WO3Nanoparticle。
Preferably, in step (1), stirring condition is magnetic agitation 5～15min, and rotating speed is 200～400r/min。
In step (2), stirring condition is for be stirred when rotating speed is 100～200r/min。
In step (3), rate of addition is 0.05～0.1ml/s。
Wherein, described high ion concentration plating solution is containing 0.5～0.2mol/LPb2+Plating solution。
In one preferred embodiment, the concentration of sodium tungstate is the concentration of 4wt%HCl solution is 20wt%, and the concentration of sodium dodecyl sulfate solution is 10wt%, and the concentration of polyacrylic acid solution is 4wt%。
By the WO that above-mentioned preparation method prepares3Nanoparticle is equally in protection scope of the present invention。
Present invention further proposes WO3Nanoparticle application in composite plating。
Beneficial effect: compared with prior art, the present invention is by selecting properly mixed sodium lauryl sulphate and polyacrylic acid as coating material, and with sodium tungstate for raw material, hydrochloric acid is as precipitant, the WO of preparation3Nanoparticle has excellent suspension in the electroplate liquid of high ion concentration (can containing 0.5～0.2mol/LPb2+Plating solution in stable suspersion), this nanoparticle has good application in composite plating, and preparation method is simple, it is easy to keeping, super quality and competitive price。
Accompanying drawing explanation
Figure 1A is the stereoscan photograph of the nanoparticle of embodiment 1 preparation, and the stereoscan photograph of the nanoparticle of Figure 1B comparative example 1 preparation；
Fig. 2 is comparative example 1 and the suspendability contrast in the plating solution of embodiment 1 product；
Fig. 3 is comparative example 1 and the contrast photo of embodiment 1 product suspension situation in the plating solution, and wherein, upper row is embodiment 1, and lower row is comparative example 1。
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method。
Embodiment 1: a kind of can in high ion concentration plating solution the WO of stable suspersion3The preparation method of nanoparticle。
First ensure that production region and equipment clean and dry, the vessel of use are cleaned up and sterilizes。
It is embodied as step as follows:
(1) by 20ml10% sodium lauryl sulphate and 10ml4% polyacrylic acid by mixing, and magnetic agitation 10min, rotating speed is 300r/min
(2) in the water-bath of 97 DEG C, above-mentioned mixed solution is joined 10mL4%Na2WO4In aqueous solution, it is stirred when rotating speed is 200r/min；
(3) under agitation, in this system, rapidly join 20mL20% hydrochloric acid solution, occur to yellow mercury oxide；
(4) reaction system at room temperature being cooled down, ultrasonic agitation is reacted 8 minutes, and supersonic frequency is 100Hz。
(5) yellow product being filtered, wash, then vacuum drying 12h under 50 DEG C of conditions, obtains WO3Nanoparticle。
Above-mentioned WO3Nanoparticle application in composite plating:
The configuration of plating solution:
Preparation 100mL0.2mol/LPb (NO3)2, 0.1mol/LHNO3Solution。The WO of 5mmol/L is added in this solution3Nanoparticle, ultrasonic agitation 10 minutes。Observe its suspension situation。
By product suspension situation in above-mentioned plating solution it can be seen that the WO for preparing of the present embodiment3Nanoparticle product dispersibility and suspension in the plating solution of high ion concentration is good, has no obvious sedimentation in 1h, occurs part sedimentation after 2h。
Embodiment 2: a kind of WO suitable in composite plating3The preparation method of nanoparticle。
Guarantee to produce region and equipment clean and dry, the vessel of use are cleaned up and sterilizes。
Preparation process substantially with embodiment 1, the difference is that:
Formula is: 20mL4wt%Na2WO4Aqueous solution, the sodium dodecyl sulfate solution of 20mL5wt%, 35mL20wt%HCl solution。
Then according to prepared by the method for embodiment 1 preparation, and it is dispersed in plating solution described in embodiment 1 to detect its suspendability。
The sodium dodecyl sulfate solution adding 20mL5% is most suitable, but remains to see obvious sedimentation。Sodium lauryl sulphate addition is too much, WO3Yield is high substantially to be reduced, and suspension is general；Sodium lauryl sulphate addition is very few, WO3Easily reuniting, suspension is poor。
Embodiment 3: a kind of WO suitable in composite plating3The preparation method of nanoparticle。
Guarantee to produce region and equipment clean and dry, the vessel of use are cleaned up and sterilizes。
Preparation process substantially with embodiment 1, the difference is that:
Formula is: 20mL2%Na2WO4Aqueous solution, the polyacrylic acid solution of 20mL2.5～30%, 35mL20%HCl solution。
Then according to prepared by the method for embodiment 1 preparation, and it is dispersed in plating solution described in embodiment 1 to detect its suspendability。
It is shown that when adding the polyacrylic acid solution of 20mL4% in experiment, and suspension is good。When polyacrylic acid addition is too much, WO3Not being easily formed, yield substantially reduces, and reaction solution is light yellow, and settles rapidly；When polyacrylic acid addition is very few, WO3Can reunite rapidly and settle。
Embodiment 4: a kind of WO suitable in composite plating3The preparation method of nanoparticle。
Guarantee to produce region and equipment clean and dry, the vessel of use are cleaned up and sterilizes。
Preparation process substantially with embodiment 1, the difference is that:
Formula is: 20mL2%Na2WO4Aqueous solution, the sodium lauryl sulphate of 10mL10%, 10mL1% polyacrylic acid solution, 35mL20%HCl solution。
Then according to prepared by the method for embodiment 1 preparation, and it is dispersed in plating solution described in embodiment 1 to detect its suspendability。
It is shown that the sodium lauryl sulphate added is appropriate, and when polyacrylic acid addition is very few, WO3Suspension is general, it does not have be obviously improved。
Embodiment 5: a kind of WO suitable in composite plating3The preparation method of nanoparticle。
Guarantee to produce region and equipment clean and dry, the vessel of use are cleaned up and sterilizes。
Preparation process substantially with embodiment 1, the difference is that:
Formula is: 20mL2%Na2WO4Aqueous solution, the sodium lauryl sulphate of 10mL10%, 10mL30% polyacrylic acid solution, 35mL20%HCl solution。
Then according to prepared by the method for embodiment 1 preparation, and it is dispersed in plating solution described in embodiment 1 to detect its suspendability。
The sodium lauryl sulphate added is appropriate, and when polyacrylic acid addition is too much, WO3Particle is not easily formed, and yield substantially reduces, and reaction solution is light yellow, and particle precipitation is very fast。
Comparative example 1:
When being not added with any coating material, in the water-bath of 97 DEG C, 40mL2%Na2WO4In aqueous solution, under agitation, in this system, rapidly join 35mL20%HCl solution, occur to yellow mercury oxide；Then by reaction system at room temperature, ultrasonic agitation is reacted 8 minutes。After reaction terminates, product filtered, wash, then under 50 DEG C of conditions, obtain yellow WO after vacuum drying 12h3Nanoparticle。
Comparative example 1 does not add any coating material, is dispersed in plating solution described in embodiment 1 by this product to detect its suspendability, its result and embodiment 1 contrast as shown in Figure 1, Figure 2 and Figure 3。
Figure 1A is embodiment 1 stereoscan photograph, and the stereoscan photograph of Figure 1B comparative example 1, contrasted from Figure 1A, B, embodiment 1 product is the nanometer sheet of 100nm × 100nm × 10nm, and favorable dispersibility, and comparative example 1 product is reunited completely, prepared nanometer sheet is intersected with each other, defines blade inserting " particle cluster "。
From Fig. 2 and Fig. 3, comparative example 1 product sedimentation velocity without any finishing is very fast, nearly reaches 100% sedimentation after 2h, and can stable suspersion in the plating solution of high ion concentration through embodiment 1 product of finishing, have no obvious sedimentation in 1h, part sedimentation occurs after 2h。Illustrate that embodiment 1 product has very big application prospect in composite plating。
The above is only the citing of embodiments of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the technology of the present invention principle; can also making some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention。

Claims (8)

1. one kind can the preparation method of tungsten trioxide nano particle of stable suspersion in high ion concentration plating solution, it is characterised in that comprise the steps:
(1) it is 3～5: 1～2 be mixed and stirred for by mass percentage by 5～15wt% sodium lauryl sulphate and 2～6wt% polyacrylic acid, obtains finishing liquid；
(2) in the water-bath of 95～100 DEG C, described finishing liquid is joined 2～6wt%Na2WO4In aqueous solution and stir, wherein, finishing liquid and Na2WO4The mass ratio of aqueous solution is 4: 1～3: 1；
(3) under agitation, in the system that step (2) obtains, in system, drip 10～30wt% hydrochloric acid solution, occur to yellow mercury oxide；
(4) reaction system that step (3) obtains at room temperature is cooled down, ultrasonic agitation；
(5) yellow product filtered, wash, after vacuum drying, obtain WO3Nanoparticle。
2. preparation method according to claim 1, it is characterised in that in step (1), stirring condition is magnetic agitation 5～15min, and rotating speed is 200～400r/min。
3. preparation method according to claim 1, it is characterised in that in step (2), stirring condition is for be stirred when rotating speed is 100～200r/min。
4. preparation method according to claim 1, it is characterised in that the concentration of sodium tungstate is the concentration of 4wt%HCl solution is 20wt%, and the concentration of sodium dodecyl sulfate solution is 10wt%, and the concentration of polyacrylic acid solution is 4wt%。
5. preparation method according to claim 1, it is characterised in that in step (3), rate of addition is 0.05～0.1ml/s。
6. preparation method according to claim 1, it is characterised in that described high ion concentration plating solution is containing 0.5～0.2mol/LPb2+Plating solution。
7. the tungsten trioxide nano particle that the preparation method described in any one of claim 1～6 prepares。
8. the application in composite plating of the tungsten trioxide nano particle described in claim 7。
CN201610018894.6A 2016-01-12 2016-01-12 In high ion concentration plating solution can stable suspersion tungsten trioxide nano particle preparation method and application Expired - Fee Related CN105692700B (en)

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Cited By (2)

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CN111041541A (en) * 2019-12-30 2020-04-21 临沂鑫海新型材料有限公司 High-performance nickel-based wear-resistant alloy
CN112103087A (en) * 2020-09-17 2020-12-18 西北大学 Method for preparing carbon quantum dot modified multistage tungsten trioxide-foamed nickel composite material and application thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111041541A (en) * 2019-12-30 2020-04-21 临沂鑫海新型材料有限公司 High-performance nickel-based wear-resistant alloy
CN112103087A (en) * 2020-09-17 2020-12-18 西北大学 Method for preparing carbon quantum dot modified multistage tungsten trioxide-foamed nickel composite material and application thereof
CN112103087B (en) * 2020-09-17 2021-10-15 西北大学 Method for preparing carbon quantum dot modified multistage tungsten trioxide-foamed nickel composite material and application thereof

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