CN101092247A - Method for preparing non-crystalline Nano composite material of Nano titania of nickel, phosphor, chrome - Google Patents
Method for preparing non-crystalline Nano composite material of Nano titania of nickel, phosphor, chrome Download PDFInfo
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- CN101092247A CN101092247A CN 200710098859 CN200710098859A CN101092247A CN 101092247 A CN101092247 A CN 101092247A CN 200710098859 CN200710098859 CN 200710098859 CN 200710098859 A CN200710098859 A CN 200710098859A CN 101092247 A CN101092247 A CN 101092247A
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Abstract
This invention relates to a method for preparing amorphous Ni-P-Cr/nanoscale TiO2 nanocomposite for preventing corrosion by seawater and sea microorganisms. The method comprises: utilizing low-toxicity Cr3+ as the Cr source, and performing DC deposition to prepare amorphous Ni-P-Cr/nanoscale TiO2 nanocomposite. The nanoscale TiO2 material is TiO2 nanowires and nanotubes prepared by using AAO template. The amorphous Ni-P-Cr/nanoscale TiO2 nanocomposite can prevent corrosion by seawater and sea microorganisms, such as sulfate reducing bacteria. The corrosion rate of the amorphous Ni-P-Cr/nanoscale TiO2 nanocomposite in SRB culture medium is 4.86X10-4 mm/a.
Description
Technical field:
The invention belongs to the anticorrosion engineering field, particularly a kind of nickel phosphorus chromium nano titanium oxide (Ni-P-Cr/nano-TiO
2) preparation method of amorphous nano matrix material, be used for anti-seawater and seawater microbiological corrosion.
Background technology:
Anti-sea-water corrosion is the problem that the whole world is attached great importance to always.And pollute in recent years and cause the eutrophication of seawater that the seawater microbial reproduction is spread unchecked, make from the seriously corroded of seawater electrolysis matter and marine microorganism two aspects affect life-span and safety such as petroleum drilling frame, naval vessel and other maritime facilitieies.Past great majority research is more multiple, and what look is the research and development of seawater corrosion resistance coating, and is its influence to material corrosion of research mostly to microbiological corrosion research, the antibiotic means that also adopt the topochemistry sterilization mostly and change the microorganism life condition.The people TiO that bactericidal property is good is arranged in recent years
2Nano particle and material combine, and give the antibacterial ability of material self, but rarely report at the research and development of the anti-corrosion new function material of seawater microorganism.
J.Novakovic etc. are at Surface﹠amp; Coating Technology, 2006, the 201:895-901 report has prepared Ni-P-TiO with chemical plating method
2Composite deposite, and studied corrosion resistance in 3.5%NaCl solution, its corrosion resistance is 51.76k Ω cm
-2, erosion rate is 0.015mm/a.And be 32.48k Ω cm with the corrosion resistance of the Ni-P alloy of quadrat method preparation
-2But they do not report that this coating has the performance of sea water resistance microbiological corrosion.
Liu Hongfang etc. are at material protection; 1999,32 (11) have reported with chemical Ni-P plating and Ni-Mo-P and can improve Q230 steel microbial corrosion resistance ability, and wherein Ni-P coating P content is 8.56wt%; P content is 4.59wt% in the Ni-Mo-P coating, and Mo content is 17.19wt%.Place the substratum medium that contains SRB to carry out corrosion test test piece, find that the Q230 steel is 0.0339mm/a in the erosion rate of the substratum medium of SRB, that Ni-P is 0.0145mm/a, and that Ni-Mo-P is 0.0438mm/a.Though its material has the performance of certain microbial corrosion resistance, effect is not fine, and and not exclusively at the seawater microbiological corrosion.
Summary of the invention
The objective of the invention is to develop a kind of characteristic that not only has good seawater corrosion resistance, also can effectively prevent to be the corrosive matrix material of marine microorganism of representative with the sulphate reducing bacteria.
A kind of nickel phosphorus chromium nano titanium oxide (Ni-P-Cr/nano-TiO
2) preparation method of amorphous nano matrix material, it is characterized in that: anode is the nickel plate, and negative electrode is the A3 steel, and the proportioning behind the electroplate liquid constant volume is: NiCl
36H
2O20.0-40.0g/L, CrCl
36H
2O 70.0-100.0g/L, Trisodium Citrate (C
6H
5Na
3O
72H
2O) 40.0-50.0g/L, H
3BO
325.0-40.0g/L, NaH
2PO
2H
2O 30.0g/L, NH
4Cl 50.0g/L, KBr10.0g/L, HCOOH 30.0-40.0ml/L.With NiCl
36H
2O, CrCl
36H
2O, Trisodium Citrate (C
6H
5Na
3O
72H
2O), H
3BO
3, NaH
2PO
2H
2O, NH
4Cl, KBr, HCOOH add that the internal diameter for preparing with the AAO template is about 40nm-60nm, external diameter is that 70nm-90nm nano TiO 2 pipe 2.0-10.0g/L or diameter are 70nm-100nm nano TiO 2 line after with the deionized water dissolving constant volume, ultra-sonic dispersion finishes with water quench to 18～22 ℃, after stablizing 30-60min, the room temperature placement begins to electroplate, mode of deposition: 18-22 ℃, depositing time 120min, current density 60-220mA/cm
2, magnetic agitation 5r/s.
AAO (anodic alumina films) template prepares TiO
2Nanotube and nano wire:
Tetrabutyl titanate and dehydrated alcohol are made into 1. number mixed solution with 1: 5 mixed, and then get dehydrated alcohol, deionized water, hydrochloric acid and be made into 2. number mixed solution with 25: 1: 0.2 mixed.In ice-water bath, magnetic agitation is 1. behind number mixed solution 8-15min, will be 2. number mixed solution slowly join 1. in number mixed solution, and to add with respect to 1.+2. mixed solution massfraction be the tensio-active agent cetyl trimethylammonium bromide (CTAB) of 0.02%-0.39%, after keeping the constant continuation of rotating speed to stir 9-15min, stop to stir, promptly make TiO
2Vitreosol.The AAO template is immersed TiO
2Take out template behind the vitreosol 15-30min, at room temperature template left standstill 120-180min, be put in then in the retort furnace be warming up to 500-700 ℃ and constant temperature 240-300min with stove after, reduce to room temperature with stove.With massfraction is that 5% NaOH solution dissolves the AAO template, and that prepare generation is TiO
2Nanotube.
Same operation, and add when 1.+2. the mixed solution massfraction is the tensio-active agent cetyl trimethylammonium bromide (CTAB) of 0.4-4%, be generated as TiO
2Nano wire.
The present invention uses the composite deposition technology, with the Cr of low toxicity from the self performance of material
3+Be the chromium source, prepare Ni-P-Cr/nano-TiO with the dc electrodeposition method
2The amorphous nano crystal composite material.Nano-TiO wherein
2Material is respectively the TiO with the preparation of AAO template
2Nano wire and nanotube.This matrix material not only has the characteristic of good seawater corrosion resistance, also can effectively prevent with the sulphate reducing bacteria to be the corrosion of the marine microorganism of representative.Ni-P-Cr/nano-TiO wherein
2Pipe is 4.86 * 10 in the erosion rate of the substratum medium of SRB
-4Mm/a.
The present invention adopts the research of composite deposition method to prepare Ni-P-Cr/tube-TiO
2And Ni-P-Cr/wire-TiO
2Composite deposite.TiO
2The pattern of nano material adopts TEM to characterize.Studied the surface topography of composite deposite and elementary composition with SEM, EDX.
In simulated seawater (3.5%NaCl) solution and sulphate reducing bacteria (SRB) corrosive medium, use the anti-corrosion and anti-microbial property that polarization curve experiment and electrochemical impedance spectrometry (EIS) institute prepare composite deposite respectively.Experimental result shows.Ni-P-Cr/tube-TiO
2The corrosion potential E of composite deposite in corrosive medium
CorrOther several coating calibrations relatively, and from corrosion current i
CorrThen less relatively, i.e. Ni-P-Cr/tube-TiO
2Composite deposite has good relatively electrolyte-resistant solution corrosion resisting property; Each composite deposite soaks back generation passivation to a certain degree at the SRB corrosive medium, can determine that each coating all has anti-corrosion and anti-microbial property.Because Ni-P-Cr/tube-TiO
2The TiO that coating is added in preparation
2Nanotube has bigger specific surface area makes Ni-P-Cr/tube-TiO
2Coating embodies the better corrosive of anti-SRB performance.
Description of drawings
Fig. 1 is example 2 composite deposite SEM Electronic Speculum figure.
Fig. 2 is the polarization curves of example 2 coating in the 3.5%NaCl aqueous solution, corresponding corrosion potential E
CorrFor-0.33V, from corrosion current i
CorrValue is 3.04 μ Acm
-2
Fig. 3 is example 2 coating soak the impedance of 1 day, 5 days and 10 days in the SRB corrosive medium complex plane figure, wherein R
s, R
p, and C
DlBe respectively solution resistance, polarization resistance and interfacial electric double layer electric capacity.Solve its polarization resistance thus and be respectively 2.84 * 10
6, 4.21 * 10
6With 5.42 * 10
6Ω cm
2, calculate erosion rate be 4.87 * 10
-4Mm/a.
Fig. 4 is example 4 composite deposite SEM Electronic Speculum figure.
Fig. 5 is the polarization curves of example 4 coating in the 3.5%NaCl aqueous solution, corresponding corrosion potential E
CorrFor-0.341V, from corrosion current i
CorrValue is 4.35 μ Acm
-2
Fig. 6 is example 4 coating soak the impedance of 1 day, 5 days and 10 days in the SRB corrosive medium complex plane figure, wherein R
s, R
p, and C
DlBe respectively solution resistance, polarization resistance and interfacial electric double layer electric capacity.Solve its polarization resistance thus and be respectively 1.82 * 10
6, 3.26 * 10
6With 3.69 * 10
6Ω cm
2, calculate erosion rate be 7.15 * 10
-4Mm/a.
Embodiment
Prepare alloy layer with direct current deposition method, anode is the square nickel plate of 30mm * 30mm * 5mm [purity is 99.99% (mass)], negative electrode is that the square A3 steel of 20mm * 20mm * 1mm (is formed mass%:C0.18%, Si0.15%, Mn0.50%, all the other are Fe, and are as follows), non-working surface seals with epoxy resins insulation, passes through processing such as polishing (to 1200 orders), oil removing and ultrasonic cleaning before the working face deposition successively.
Example 1:Ni-P-Cr/nano-TiO
2The preparation of nanotube amorphous nano composite deposite and the performance of sea water resistance microbiological corrosion
Nano-TiO
2Fresh plating bath is prepared in the preparation of pipe suspension plating bath: NiCl36H2O 38.0g/L, CrCl36H2O 95.0g/L, C6H5Na3O72H2O 45.0g/L, H3BO3 38.0g/L, NaH2PO2H2O30.0g/L, NH4Cl 50.0g/L, KBr 10.0g/L, HCOOH 38.0ml/L.Add the nano TiO 2 pipe 5.0g/L (internal diameter is about 50nm, external diameter 80nm) for preparing with the AAO template behind plating bath dissolving and the constant volume, when ultra-sonic dispersion finishes with water quench to 18～22 ℃, at 180mA/cm
2, depositing time 120min.
Example 2:Ni-P-Cr/nano-TiO
2The preparation of nanotube amorphous nano composite deposite and the performance of sea water resistance microbiological corrosion
Nano-TiO
2Fresh plating bath is prepared in the preparation of pipe suspension plating bath: NiCl36H2O 25.0g/L, CrCl36H2O 75.0g/L, C6H5Na3O72H2O 45.0g/L, H3BO3 28.0g/L, NaH2PO2H2O30.0g/L, NH4Cl 50.0g/L, KBr 10.0g/L, HCOOH 38.0ml/L.Add the nano TiO 2 pipe 5.0g/L (internal diameter is about 50nm, external diameter 80nm) for preparing with the AAO template behind plating bath dissolving and the constant volume, when ultra-sonic dispersion finishes with water quench to 18～22 ℃, at 180mA/em
2, depositing time 120min.
The composite deposite that plates out with example 2 is an example, has described that it is elementary composition, surface topography and corrosion resistance nature.
Elementary composition, the surface topography of composite deposite
Elementary composition (w/w) that measure composite deposite with energy spectrometer is Ni15.90%, P21.76%, Cr60.11%, Ti2.23%.
Corrosion resistance nature
The experimental system of polarization curve test is that mass percent is 3.5% the NaCl aqueous solution, and the sample useful area is 1.0cm
2, counter electrode is large-area gauze platinum electrode, reference electrode is saturated calomel electrode (following current potential is all with respect to saturated calomel electrode), uses Luggin capillary to reduce solution I R and falls.Experiment is at room temperature carried out, and instrument is U.S. EG﹠amp; G PARC M273 potentiostat, test macro is a M352 corrosion test software, sweeps speed and is 0.266mV/s.
Impedance (EIS) experiment is that corrosive medium carries out with the substratum that contains SRB.Substratum consists of: Na
2SO
40.5g/L, NH
4Cl 1.0g/L, CaCl
20.1g/L, K
2HPO
40.5g/L, MgSO
42.0g/L, Sodium.alpha.-hydroxypropionate 3.5g/L, Yeast diffusion juice 1.0g/L.Regulating the pH value is 7.0～7.2, and at 121 ℃ of steam sterilizing 20min, the cooling back adds ferrous ammonium sulphate (0.1g/L) and the xitix (0.1g/L) through 0.22 μ m membrane filtration degerming.Anaerobic is cultivated and is soaked after inoculation SRB and the logical nitrogen deoxygenation.Instrument is U.S. EG﹠amp; G PARC M273 potentiostat and 5208 lock-in amplifiers, system is a M388 ac impedance measurement software.Test under open circuit potential, the AC sine wave amplitude is 10mV, and range of frequency is 10
5～10
-3Hz, wherein HFS is finished by lock-in amplifier, and low frequency part is finished by potentiostat.Experiment is at room temperature carried out, and carries out the EIS test first time after successive soaking, sample soak and stablized in about 2 hours, carries out totally 3 EIS tests in 5 days and 10 days in immersion respectively thereafter.
Example 3 Ni-P-Cr/nano-TiO
2The preparation of nano wire amorphous nano composite deposite and the performance of sea water resistance microbiological corrosion
Nano-TiO
2Fresh plating bath is prepared in the preparation of line suspension plating bath: NiCl36H2O 38.0g/L, CrCl36H2O 95.0g/L, C6H5Na3O72H2O 45.0g/L, H3BO3 38.0g/L, NaH2PO2H2O30.0g/L, NH4Cl 50.0g/L, KBr 10.0g/L, HCOOH 38.0ml/L.Adding the nano TiO 2 line 5.0g/L diameter for preparing with the AAO template behind plating bath dissolving and the constant volume is 70nm-100nm, when ultra-sonic dispersion finishes with water quench to 18～22 ℃, at 180mA/cm
2, depositing time 120min.
Example 4 Ni-P-Cr/nano-TiO
2The preparation of nano wire amorphous nano composite deposite and the performance of sea water resistance microbiological corrosion
Nano-TiO
2Fresh plating bath is prepared in the preparation of line suspension plating bath: NiCl36H2O 25.0g/L, CrCl36H2O 75.0g/L, C6H5Na3O72H2O 45.0g/L, H3BO3 28.0g/L, NaH2PO2H2O30.0g/L, NH4Cl 50.0g/L, KBr 10.0g/L, HCOOH 38.0ml/L.Adding the nano TiO 2 line 5.0g/L diameter for preparing with the AAO template behind plating bath dissolving and the constant volume is 70nm-100nm, when ultra-sonic dispersion finishes with water quench to 18～22 ℃, at 180mA/cm
2, depositing time 120min.
The composite deposite that plates out with example 4 is an example, has described that it is elementary composition, surface topography and corrosion resistance nature.
Elementary composition, the surface topography of composite deposite
Elementary composition (w/w) that measure composite deposite with energy spectrometer is Ni17.35%, P26.42%, Cr53.66%, Ti2.57%.
Corrosion resistance nature
The experimental system of polarization curve test is that mass percent is 3.5% the NaCl aqueous solution, and the sample useful area is 1.0cm
2, counter electrode is large-area gauze platinum electrode, reference electrode is saturated calomel electrode (following current potential is all with respect to saturated calomel electrode), uses Luggin capillary to reduce solution I R and falls.Experiment is at room temperature carried out, and instrument is U.S. EG﹠amp; G PARCM273 potentiostat, test macro are M352 corrosion test software, sweep speed and are 0.266mV/s.
Impedance (EIS) experiment is that corrosive medium carries out with the substratum that contains SRB.Substratum consists of: Na
2SO
40.5g/L, NH
4Cl 1.0g/L, CaCl
20.1g/L, K
2HPO
40.5g/L, MgSO
42.0g/L, Sodium.alpha.-hydroxypropionate 3.5g/L, Yeast diffusion juice 1.0g/L.Regulating the pH value is 7.0～7.2, and at 121 ℃ of steam sterilizing 20min, the cooling back adds ferrous ammonium sulphate (0.1g/L) and the xitix (0.1g/L) through 0.22 μ m membrane filtration degerming.Anaerobic is cultivated and is soaked after inoculation SRB and the logical nitrogen deoxygenation.Instrument is U.S. EG﹠amp; G PARC M273 potentiostat and 5208 lock-in amplifiers, system is a M388 ac impedance measurement software.Test under open circuit potential, the AC sine wave amplitude is 10mV, and range of frequency is 10
5～10
-3Hz, wherein HFS is finished by lock-in amplifier, and low frequency part is finished by potentiostat.Experiment is at room temperature carried out, and carries out the EIS test first time after successive soaking, sample soak and stablized in about 2 hours, carries out totally 3 EIS tests in 5 days and 10 days in immersion respectively thereafter.
Claims (3)
1. the preparation method of a non-crystalline Nano composite material of Nano titania of nickel, phosphor, chrome, it is characterized in that: anode is the nickel plate, and negative electrode is the A3 steel, and the proportioning behind the electroplate liquid constant volume is: NiCl
36H
2O:20.0-40.0g/L, CrCl
36H
2O:70.0-100.0g/L, C
6H
5Na
3O
72H
2O:40.0-50.0g/L, H
3BO
3: 25.0-40.0g/L, NaH
2PO
2H
2O:30.0g/L, NH
4Cl:50.0g/L, KBr:10.0g/L, HCOOH:30.0-40.0ml/L: with NiCl
36H
2O, CrCl
36H
2O, C
6H
5Na
3O
72H
2O, H
3BO
3, NaH
2PO
2H
2O, NH
4It is that 40nm-60nm, external diameter are that 70nm-90nm nano TiO 2 pipe 2.0-10.0g/L or diameter are 70nm-100nm nano TiO 2 line that Cl, KBr, HCOOH add the internal diameter for preparing with the AAO template after with the deionized water dissolving constant volume, ultra-sonic dispersion finishes with water quench to 18～22 ℃, after stablizing 30-60min, the room temperature placement begins to electroplate, mode of deposition: 18-22 ℃, depositing time 120min, current density 60-220mA/cm
2, magnetic agitation 5r/s.
2. a kind of preparation method of non-crystalline Nano composite material of Nano titania of nickel, phosphor, chrome according to claim 1, the method that it is characterized in that the nano TiO 2 pipe of AAO template preparation is: tetrabutyl titanate and dehydrated alcohol are made into 1. number mixed solution with 1: 5 mixed, and then get dehydrated alcohol, deionized water, hydrochloric acid and be made into 2. number mixed solution with 25: 1: 0.2 mixed; In ice-water bath, magnetic agitation is 1. behind number mixed solution 8-15min, will be 2. number mixed solution join 1. in number mixed solution, and to add with respect to 1.+2. mixed solution massfraction be the tensio-active agent cetyl trimethylammonium bromide of 0.02%-0.39%, after keeping the constant continuation of rotating speed to stir 9-15min, stop to stir, promptly make TiO
2Vitreosol; The AAO template is immersed TiO
2Take out template behind the vitreosol 15-30min, at room temperature template left standstill 120-180min, be put in then in the retort furnace be warming up to 500-700 ℃ and constant temperature 240-300min with stove after, reduce to room temperature with stove; With massfraction is that 5% NaOH solution dissolves the AAO template, prepares the TiO of generation
2Nanotube.
3. a kind of preparation method of non-crystalline Nano composite material of Nano titania of nickel, phosphor, chrome according to claim 1, the method that it is characterized in that the nano TiO 2 pipe of AAO template preparation is: tetrabutyl titanate and dehydrated alcohol are made into 1. number mixed solution with 1: 5 mixed, and then get dehydrated alcohol, deionized water, hydrochloric acid and be made into 2. number mixed solution with 25: 1: 0.2 mixed; In ice-water bath, magnetic agitation is 1. behind number mixed solution 8-15min, will be 2. number mixed solution join 1. in number mixed solution, and to add with respect to 1.+2. mixed solution massfraction be the tensio-active agent cetyl trimethylammonium bromide of 0.4-4%, after keeping the constant continuation of rotating speed to stir 9-15min, stop to stir, promptly make TiO
2Vitreosol; The AAO template is immersed TiO
2Take out template behind the vitreosol 15-30min, at room temperature template left standstill 120-180min, be put in then in the retort furnace be warming up to 500-700 ℃ and constant temperature 240-300min with stove after, reduce to room temperature with stove; With massfraction is that 5% NaOH solution dissolves the AAO template, prepares the TiO of generation
2Nano wire.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613080B (en) * | 2009-07-23 | 2011-03-23 | 重庆大学 | Method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN102260414A (en) * | 2010-05-21 | 2011-11-30 | 冀州市中意复合材料有限公司 | Material with reef-like structure and preparation method thereof |
| CN102358949A (en) * | 2011-09-28 | 2012-02-22 | 中国人民解放军91872部队上海研究室 | Aluminium alloy anticorrosion treatment technology |
| CN102502484A (en) * | 2011-09-28 | 2012-06-20 | 重庆大学 | Modified titanium dioxide nano particle nanotube and preparation method thereof |
| CN105386089A (en) * | 2015-12-25 | 2016-03-09 | 武汉迪赛环保新材料股份有限公司 | Trivalent chromium hard chromium electroplating solution and application of trivalent chromium hard chromium electroplating solution in hard chromium electroplating |
-
2007
- 2007-04-28 CN CNB2007100988590A patent/CN100546916C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613080B (en) * | 2009-07-23 | 2011-03-23 | 重庆大学 | Method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN102260414A (en) * | 2010-05-21 | 2011-11-30 | 冀州市中意复合材料有限公司 | Material with reef-like structure and preparation method thereof |
| CN102260414B (en) * | 2010-05-21 | 2013-01-09 | 冀州市中意复合材料有限公司 | Material with reef-like structure and preparation method thereof |
| CN102358949A (en) * | 2011-09-28 | 2012-02-22 | 中国人民解放军91872部队上海研究室 | Aluminium alloy anticorrosion treatment technology |
| CN102502484A (en) * | 2011-09-28 | 2012-06-20 | 重庆大学 | Modified titanium dioxide nano particle nanotube and preparation method thereof |
| CN102502484B (en) * | 2011-09-28 | 2014-05-28 | 重庆大学 | Modified titanium dioxide nano particle nanotube and preparation method thereof |
| CN105386089A (en) * | 2015-12-25 | 2016-03-09 | 武汉迪赛环保新材料股份有限公司 | Trivalent chromium hard chromium electroplating solution and application of trivalent chromium hard chromium electroplating solution in hard chromium electroplating |
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| Publication number | Publication date |
|---|---|
| CN100546916C (en) | 2009-10-07 |
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