CN104312333A - Anti-corrosion and conductive coating rich in nickle and preparation method of coating - Google Patents
Anti-corrosion and conductive coating rich in nickle and preparation method of coating Download PDFInfo
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention relates to anti-corrosion and conductive coating rich in nickle and a preparation method of the coating. The anti-corrosion and conductive coating is prepared by adopting the following components in parts by weight: 300-450 parts of a film-forming substance, 100-400 parts of a conductive filler, 150-225 parts of a solvent, 90-135 parts of a curing agent, 30-45 parts of a plasticizing agent and 30-45 parts of a defoaming agent, wherein the conductive filler is nickle powder and the content of the conductive filler in a compound system is 10-40wt%. Compared with the prior art, the anti-corrosion and conductive coating and the preparation method have the advantages that an optimum formula for preparing the anti-corrosion and conductive coating is determined by adopting the nickle powder and acrylic acid as main materials; in the anti-corrosion and conductive coating, the larger the filling mass of the nickle powder is, the better the electrical conductivity of the coating is and the poorer the corrosion resistance is; by comprehensive consideration of the electrical conductivity and the anti-corrosion performance of the coating, the percent of the filling mass of the nickle powder is about 18%, not only is the electrical conductivity better, but also the excellent anti-corrosion performance is shown.
Description
Technical field
The invention belongs to corrosion and protection technical field, especially relate to a kind of rich nickel corrosion-resistant conductive coating and preparation method thereof.
Background technology
Grounding net of transformer substation is the indispensable facility for working grounding, grounding for lightening, protective ground, is the important step guaranteeing the person, equipment, security of system, and it plays a part earial drainage at thunder-lightning, electrostatic and fault current and all presses.
Earthing pole is destroyed because being subject to galvanic corrosion in soil, and in the soil that corrodibility is serious, earthing pole will be corroded totally in several years.Many ground connectoies do not consider anticorrosive measure, run Grounding Grid for many years serious, can not meet thermally-stabilised requirement, when be short-circuited accident time, earth mat blows, and ground potential raises, and high pressure seals in secondary circuits, makes fault spread, causes heavy economic losses.
Generally adopt steel to be earthing material in the world at present, China and many countries also adopt steel, and the U.S. and some European countries then adopt copper material, and copper erosion resistance is better, but expensive, and cost of investment increases by 5 ~ 6 times, and easily galvanic corrosion occurs.Steel is as ground connector, thermostability comparatively copper is good, low price, but its corrosion resistance nature is poor, for improving its corrosion resistance nature, method the most frequently used at present adopts galvanized steel to slow down to make corrosion speed, but in the soil that corrodibility is serious, zinc coating is corroded very soon, fundamentally cannot solve etching problem, and developing the coating having solidity to corrosion and conducting function concurrently is that the etching problem solving earthing material provides new way.
At present, the more electrically conducting coating of research has silver system, copper system, nickel system, charcoal system etc. both at home and abroad.Nickel system conductive filler material is due to moderate cost, and conductive effect is also better, and chemical stability has well been applied to a lot of field.Resin in electrically conducting coating commonly uses acrylic resin and urethane.Wherein conventional with nickel-acrylic resin systems.
Chinese patent CN103333574A discloses one and can at high temperature use and corrosion resistant coating; Still there is physical strength strong when at high temperature using, strong adhesion, corrosion resistant coating; Raw material is adopted to comprise base-material, solvent, solidifying agent, color stuffing, silane coupling agent, siccative, auxiliary agent.Electrically conducting coating refers to that specific conductivity is greater than 10
-12s/m, there is the functional coating of semi-conductor or conductor performance.Electrically conducting coating can be divided into four large classes according to application characteristic: 1. as the coating that electrical conductor uses, have the ability of conduction current; 2. anti-shielding conductive coating, can radio wave shield, hertzian wave etc.; 3. antistatic coating; 4. other, as Electro-Discolor Coating, photoconductive coating.Can at high temperature use and corrosion resistant coating disclosed in this patent, it is anti-shielding coating, can the radiowave and hertzian wave etc. of radiation-screening, this and rich nickel corrosion-resistant conductive coating disclosed in the present application, there is corrosion resistance nature, have the ability of conduction current, the coating used as electrical conductor is not identical.
Summary of the invention
Object of the present invention is exactly provide a kind of existing good conductivity, rich nickel corrosion-resistant conductive coating showing again excellent antiseptic property and preparation method thereof to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A kind of rich nickel corrosion-resistant conductive coating, adopts the raw material of following component and weight part content to prepare:
Filmogen 300-450, conductive filler material 100-400, solvent 150-225, solidifying agent 90-135, softening agent 30-45, defoamer 30-45, wherein, described conductive filler material is nickel powder, and the content in compound system is 10-40wt%.
Preferably, filmogen is high viscosity acrylic resin is pH=6-7, solid content 49 ± 1%, outward appearance is milky white liquid, viscosity is 17-19s/ normal temperature, the ACRYLIC EMULSION of T4 cup or pH=7-8, solid content 49 ± 1%, outward appearance is milky white liquid, and viscosity is the ACRYLIC EMULSION of 5000-9000CP.S.
Preferably, the content of conductive filler material is preferably 10-18wt%.
Preferably, the particle diameter of nickel powder is 200 ~ 300 orders, and nickel powder is conductive filler material, and the fineness of filler directly affects the dip-coating performance of coating, corrosion resisting property and conductivity.When packing material size is larger, the dip-coating poor-performing of coating, coating pin hole is more, and compactness is poor, and cause coating impervious poor, solidity to corrosion is bad.Filler is thinner, and its surface-area is larger, and the electroconductibility of coating is better; But filler fineness increases, and its Surface Oxygen voltinism will be aggravated, and the oxide compound of Surface Creation can cause the electroconductibility of coating to reduce.Consider, the particle diameter of filler is advisable at 200 ~ 300 orders.
As the embodiment be more preferably, nickel powder particle diameter is 250 orders.
Preferably, solvent is n-propyl alcohol and/or propyl carbinol.
Preferably, solidifying agent is commercially available solidifying agent T31.
Preferably, softening agent is dibutyl phthalate.
Preferably, defoamer is ethyl acetate.
The preparation method of rich nickel corrosion-resistant conductive coating adopts following steps: join in filmogen by solvent, solidifying agent, softening agent and defoamer, then nickel powder is added, stirrer is used to stir 20-40min with the speed of 4000r/min, nickel powder is uniformly dispersed in filmogen, during stirring, adds granulated glass sphere, grinding nickel powder, the fineness of nickel powder is controlled below 20 microns, after stirring terminates, use filter net cloth to filter and remove granulated glass sphere, namely prepare rich nickel corrosion-resistant conductive coating.
Compared with prior art, the present invention, based on nickel powder and vinylformic acid, determines the optimum formula preparing corrosion-resistant conductive coating; In corrosion-resistant conductive coating, nickel powder filling quality is larger, and the electroconductibility of coating is better, and solidity to corrosion is poorer.Consider electroconductibility and the antiseptic property of coating, nickel powder filling quality mark is about 18% time, existing good conductivity, show again excellent antiseptic property, as seen from Figure 1, as nickel powder filling quality mark very little (< 10%), the surface contacted resistance of coating is very large, and coating is almost in state of insulation.This is because when nickel powder filling quality mark is less, the separate distribution of conductive filler particles, is difficult to form conductive network structure.When nickel powder filling quality mark is 10%, the resistivity of coating is 0.225 Ω/cm
2; When nickel powder filling quality mark increases to 15%, the surface resistivity of coating reduces a lot; Then along with the further increase of nickel powder content, surface resistivity fall slows down gradually.Result of study shows, the conductivity principle of addition type conductive polymers mainly contains " seepage effect " and " tunnel effect " two kinds of mechanism and controls.
Quantum-mechanical " tunnel effect " is thought, when the non-conductive layer spacing between two conducting particless is very little (≤10nm), under electric field action, electronics can be crossed potential barrier and flow.
Seepage effect theory think occur this phenomenon be due to along with nickel powder filling quality mark increase, the probability that nickel powder particle forms conductive network structure is increasing, the gap of particle is more and more less, at this moment add again a small amount of filler just can original spacing not very very greatly, discontinuous network structure bridge joint again, network structure is linked up, and the conductivity of coating is sharply strengthened.After exceeding percolation threshold (representing with the eigenwert of nickel powder filling quality mark), the conductive filler particles newly added mainly participates in the network structure formed, and obviously reduces the contribution forming new conductive channel.Therefore, when nickel powder filling quality mark is greater than after 15%, the reduction of the surface resistivity of coating is comparatively mild.
Can observe from Fig. 2,3,4, nickel powder filling quality mark is larger, and capacitive reactance arc radius is less, illustrates that the corrosion resisting property of coating is poorer.The solidification process of coating is dehydration solidification, and the moisture of coat inside can be scattered and disappeared by the micropore in coating, is therefore also just present in micropore in coating after hardening.From the structure of coating, the filling quality mark of nickel powder is larger, and the relative content of acrylic resin is less.Acrylic resin plays cohesive action between nickel powder, forms an organic layer.Because organic layer is very thin, therefore electrolyte solution is easy to infiltrate coating, causes forming more ionic channel in coating, coating resistance is declined, cause the local corrosion of protected matrix.
Accompanying drawing explanation
Fig. 1 is the surface contact resistivity of conductive coating and the graph of a relation of nickel powder content;
Fig. 2 is the electrochemical impedance spectrogram that different coating is soaked 2 days in NaCl solution;
Fig. 3 is the electrochemical impedance spectrogram that different coating is soaked 6 days in NaCl solution;
Fig. 4 is the electrochemical impedance spectrogram that different coating is soaked 36 days in NaCl solution;
The coating of Fig. 5 to be Ni content be 10wt% in NaCl solution with the electrochemical impedance spectrogram soaking number of days;
The coating of Fig. 6 to be Ni content be 20wt% in NaCl solution with the electrochemical impedance spectrogram soaking number of days;
The coating of Fig. 7 to be Ni content be 30wt% in NaCl solution with the electrochemical impedance spectrogram soaking number of days;
The coating of Fig. 8 to be Ni content be 40wt% in NaCl solution with the electrochemical impedance spectrogram soaking number of days;
Fig. 9 is different coating | Z|
0.05with the variation diagram of soak time;
Figure 10 is the polarization curve of different coating;
The SEM photo of Figure 11 to be Ni content be coating of 10wt%;
The SEM photo of Figure 12 to be Ni content be coating of 40wt%.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
A kind of rich nickel corrosion-resistant conductive coating, adopts the raw material of following component and weight part content to prepare:
High viscosity acrylic resin is as filmogen 300-450, conductive filler material nickel powder 100-400, n-propyl alcohol and/or propyl carbinol are as solvent 150-225, solidifying agent T3190-135, plasticizer phthalic acid dibutylester 30-45, defoamer ethyl acetate 30-45, wherein, the content of nickel powder in compound system is 10-40wt%.
Solvent, solidifying agent, softening agent and defoamer are joined in filmogen, then nickel powder is added, stirrer is used to stir 20-40min with the speed of 4000r/min, nickel powder is uniformly dispersed in filmogen, during stirring, adds granulated glass sphere, grinding nickel powder, the fineness of nickel powder is controlled below 20 microns, after stirring terminates, use filter net cloth to filter and remove granulated glass sphere, namely prepare rich nickel corrosion-resistant conductive coating.
It is below concrete embodiment.
Embodiment 1-4
In full-bodied acrylic resin, add dispersion agent, defoamer, softening agent and nickel powder etc., prepare the protective system with conducting function.The paint of different nickel powder filling quality mark on carbon steel coupon, make electrode, then electrode is dipped in certain density sodium chloride solution, adopt alternating-current impedance, Tafel polarization curve, the methods such as SEM, the content of research nickel powder and coating electroconductibility, corrosion proof relation.
Experimental technique is as follows:
1, the corrosion-resistant conductive coating that nickel powder filling quality mark is respectively 10%, 20%, 30%, 40% is prepared.Its formula is as shown in table 1 ~ 4.
Table 1 nickel powder filling quality mark is the formulation for coating material of 10%
Table 2 nickel powder filling quality mark is the formulation for coating material of 20%
Table 3 nickel powder filling quality mark is the formulation for coating material of 30%
Table 4 nickel powder filling quality mark is the formulation for coating material of 40%
2, these four kinds of paint on carbon steel coupon, test its electroconductibility and solidity to corrosion.
A, use VICTOR VC830L type digital multimeter surface measurements contact resistance.
In laboratory, on the 20# carbon steel coupon of 5cm × 2.5cm, two sides is coated with electrically conducting coating, two thin carbon steel coupon right-angled intersections, naturally contact (not another plus-pressure) is placed up and down, average contact resistance (being two-sided) R is measured by the digital watch of precision 0.01 Ω, every surface resistance R/2, Units of Account contact area resistance is R/ (2 × 2.5 × 2.5).
B, employing alternating-current impedance, Tafel polarization curve, the methods such as SEM, the solidity to corrosion of research different coating in sodium chloride solution.
Electrochemistry experiment adopts three-electrode system, and working electrode is galvanized steel electrode, and supporting electrode and reference electrode are platinum electrode and the saturated calomel electrode (SCE) of Shanghai Precision Scientific Apparatus Co., Ltd's production.The 2273 type electrochemical workstations that electrochemical measurement uses A Meiteke company limited of the U.S. to produce.Electrochemical impedance spectroscopy survey frequency scope is 0.05Hz ~ 100kHz, and ac-excited signal peak is 5mV; Polarization curve scanning speed is 1mV/s, and scanning current potential is-0.35 ~-0.15V.
Adopt the SU-1500 type scanning electronic microscope all-in-one of HIT to analyze the galvanized steel electrode sample superficial film pattern after coated with conductive coating, acceleration voltage is 15kV.Herein, current potential is all relative to SCE, and all experiments are all at room temperature tested.
Test result:
Content and coating electroconductibility, the corrosion proof relation of nickel powder are described below in conjunction with data and figure.
1, surface contacted resistance
Found by research, the surface contact resistivity of conductive coating declines gradually with the increase of nickel powder consumption, then tends towards stability, as shown in Figure 1.
As seen from Figure 1, as nickel powder filling quality mark very little (< 10%), the surface contacted resistance of coating is very large, and coating is almost in state of insulation; When nickel powder filling quality mark is 10%, the resistivity of coating is 0.225 Ω/cm2; When nickel powder filling quality mark increases to 15%, the surface resistivity of coating reduces a lot; Then along with the further increase of nickel powder content, surface resistivity fall slows down gradually.
2, the impedance spectrum feature of coating system
Prepare nickel powder filling quality mark herein and be respectively 10%, 20%, 30%, the corrosion-resistant conductive coating of 40%, paint on electrode, dried, be then immersed in NaCl solution.
Different coating soaks the electrochemical impedance spectroscopy of identical number of days as Fig. 2 in NaCl solution, and 3, shown in 4, due in Fig. 2-4, in every width figure, (a) represents the Nyquist figure of coating, and (b) represents the phase diagram of coating, and (c) represents the phase angle figure of coating.
From Fig. 2,3, in 4, (a) can find out, the capacitive reactance arc radius of spectrogram changes with the difference of coating.Nickel powder filling quality mark is larger, and capacitive reactance arc radius is less.What capacitive reactance arc radius was maximum is nickel powder filling quality mark w (Ni) is the coating of 10%, and resistance value is maximum, shows that corrosive medium is long through the time needed for coating, and corrosion resistance is large, and anticorrosion ability is good; Next is w (Ni) is the coating of 20%; Be w (Ni) be again the coating of 30%; W (Ni) is the coating of 40%, and corrosion resistance is minimum.
From Fig. 2,3, in 4, (b) can find out, at full frequency band, w (Ni) be 10% coating and w (Ni) be the impedance of the coating of 20% be the coating of 30% apparently higher than w (Ni), w (Ni) is the impedance of the coating of 30% is the coating of 40% apparently higher than w (Ni).
From Fig. 2,3, in 4, (c) can find out, at high-frequency region (near 100kHz), with the increase of nickel powder filling quality mark, the phasing degree of coating declines successively, illustrates in identical soak cycle, corrosive medium more easily gos deep into the higher coat inside of nickel powder filling quality mark, thus accelerates coating failure.
The electrochemical impedance spectroscopy of same coating in NaCl solution over time as Fig. 5, (with the commentary in aforementioned Fig. 2-4, please further illustrating picture be supplement) shown in 6,7,8.
In every width figure, (a) represents the Nyquist figure of coating, and (b) represents the phase diagram of coating, and (c) represents the phase angle figure of coating.
From Fig. 5,6,7, in 8, (a) can observe, and with the prolongation of soak time, the capacitive reactance arc radius of different coating declines gradually; Nickel powder filling quality mark is larger, and it is faster that the capacitive reactance arc radius of coating declines.
From Fig. 5,6,7, in 8, (b) can observe, and with the prolongation of soak time, the impedance of different coating declines gradually; Nickel powder filling quality mark is larger, and it is faster that the impedance of coating declines.
From Fig. 5,6,7, in 8, (c) can observe, and with the prolongation of soak time, the phasing degree of different coating declines gradually; Nickel powder filling quality mark is larger, and it is faster that the phasing degree of coating declines.
The coating of different nickel powder filling quality mark | Z|
0.05with soak time change as shown in Figure 9.
Usually, Impedance Membrane value during frequency f=0.05Hz can be used | Z|
0.05relatively compare the size of the corrosion resisting property of different coating, | Z|
0.05be worth larger, the corrosion resisting property of coating is better.As can be seen from Figure 9, nickel powder filling quality mark is higher, coating | Z|
0.05be worth less; Nickel powder filling quality mark is higher, coating | Z|
0.05it is faster that value declines.
Tafel polarization curve is studied
Nickel powder filling quality mark be 10%, 40% coating in NaCl solution, soak the polarization curve after for some time as shown in Figure 10, extrapolated by the Tafel district of polarization curve, the fitting data obtained is as shown in table 5.
The Tafel result of table 5 different coating in NaCl solution
As can be seen from Table 5, increase with nickel powder filling quality mark, corrosion potential is shuffled slightly, but corrosion current has obvious increase, and erosion rate increases, and the solidity to corrosion of coating reduces.
Sem analysis
Nickel powder filling quality mark be 10%, 40% coating in NaCl solution, soak the SEM after same time as shown in Figure 11,12.As can be seen from Figure 11,12, w (Ni) be 10% coating have small crack; W (Ni) be 40% coatingsurface there is wider crack, corrosion is more serious.
This shows, in NaCl solution, with the increase of nickel powder filling quality mark, corrosion resistance coating reduces.
The viscosity of the coating prepared by the method the chances are 80 ~ 95s/ normal temperature, T4 cup.
The technical parameter of corrosion-resistant conductive coating of the present invention
| Project | Index | The method of inspection |
| Paint film appearance and color | Paint film is smooth, and color meets model | GB/T6751-1986 |
| Viscosity, s | 80-95 | GB/T1723-1993 |
| Cross cut test≤ | 1 grade | GB/T9286-1998 |
Corrosion-resistant conductive coating dip-coating is to the parameter on electrode
Electrode is immersed in corrosion-resistant conductive coating, leaves standstill about 10s, take out, 1. surface drying about 10 minutes at normal temperatures, take out; 2. put into the baking oven drying about 10 minutes of 50 DEG C, take out; 3. put into the baking oven drying about 30 minutes of 80 DEG C, take out, electrode has just prepared.
Nickel powder filling quality mark be 10% corrosion-resistant conductive coating represent with S1;
Nickel powder filling quality mark be 10% corrosion-resistant conductive coating represent with S2;
Nickel powder filling quality mark be 10% corrosion-resistant conductive coating represent with S3;
Nickel powder filling quality mark be 10% corrosion-resistant conductive coating represent with S4.
According to the tack of GB/T9286-1998 cross cut test test S1-S4.It is as shown in the table for test result
| Project | S1 | S2 | S3 | S4 |
| Cross cut test, level | 0 | 0 | 0 | 1 |
Claims (9)
1. a rich nickel corrosion-resistant conductive coating, is characterized in that, this electrically conducting coating adopts the raw material of following component and weight part content to prepare:
Filmogen 300-450, conductive filler material 100-400, solvent 150-225, solidifying agent 90-135, softening agent 30-45, defoamer 30-45, wherein, described conductive filler material is nickel powder, and the content in compound system is 10-40wt%.
2. the rich nickel corrosion-resistant conductive coating of one according to claim 1, it is characterized in that, described filmogen is high viscosity acrylic resin is pH=6-7, solid content 49 ± 1%, outward appearance is milky white liquid, and viscosity is 17-19s/ normal temperature, the ACRYLIC EMULSION of T4 cup or pH=7-8, solid content 49 ± 1%, outward appearance is milky white liquid, and viscosity is the ACRYLIC EMULSION of 5000-9000CP.S.
3. the rich nickel corrosion-resistant conductive coating of one according to claim 1, it is characterized in that, the content of described conductive filler material is preferably 10-18wt%.
4. the rich nickel corrosion-resistant conductive coating of one according to claim 1, is characterized in that, the particle diameter of described nickel powder is 200 ~ 300 orders.
5. the rich nickel corrosion-resistant conductive coating of one according to claim 1, is characterized in that, described solvent is n-propyl alcohol and/or propyl carbinol.
6. the rich nickel corrosion-resistant conductive coating of one according to claim 1, is characterized in that, described solidifying agent is commercially available solidifying agent T31.
7. the rich nickel corrosion-resistant conductive coating of one according to claim 1, is characterized in that, described softening agent is dibutyl phthalate.
8. the rich nickel corrosion-resistant conductive coating of one according to claim 1, is characterized in that, described defoamer is ethyl acetate.
9. the preparation method of the rich nickel corrosion-resistant conductive coating according to any one of claim 1-8, it is characterized in that, the method adopts following steps: join in filmogen by solvent, solidifying agent, softening agent and defoamer, then nickel powder is added, stirrer is used to stir 20-40min with the speed of 4000r/min, nickel powder is uniformly dispersed in filmogen, granulated glass sphere is added during stirring, grinding nickel powder, the fineness of nickel powder is controlled below 20 microns, after stirring terminates, use filter net cloth to filter and remove granulated glass sphere, namely prepare rich nickel corrosion-resistant conductive coating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038446A (en) * | 2015-06-04 | 2015-11-11 | 上海电力学院 | Water-based anticorrosive conducting paint and preparation method thereof |
| CN107325611A (en) * | 2017-06-28 | 2017-11-07 | 安徽慕曼德家具有限公司 | A kind of furniture anticorrosive paint additive |
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| CN107325611A (en) * | 2017-06-28 | 2017-11-07 | 安徽慕曼德家具有限公司 | A kind of furniture anticorrosive paint additive |
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