CN103173045A - Inorganic zinc-rich anticorrosive nano-attapulgite coating and its preparation method - Google Patents
Inorganic zinc-rich anticorrosive nano-attapulgite coating and its preparation method Download PDFInfo
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Abstract
The invention discloses an inorganic zinc-rich anticorrosive nano-attapulgite coating. The inorganic zinc-rich anticorrosive nano-attapulgite coating is obtained through mixing a component A and a component B according to a component A/component B mass ratio of 1:2-4, 100% by mass of the component A comprises 68-87% by mass of an inorganic adhesive, 8-30% by mass of a synthetic resin emulsion, 1.5-4% by mass of a wetting dispersant and 0.5-2% by mass of an antifoaming agent; and 100% by mass of the component B is composed of 85-98% by mass of zinc powder and 2-15% by mass of nano-attapulgite. The inorganic zinc-rich anticorrosive nano-attapulgite coating has the advantages of strong adhesion with a metal base, good flexibility, good salt spray resistance, good impact resistance and the like, and can be used in various different situations. The invention also discloses a preparation method of the inorganic zinc-rich anticorrosive nano-attapulgite coating. The preparation method has the advantages of good controllability, easy operation, low production cost and easy industrialized production.
Description
Technical field
The present invention relates to the protective system field, being specifically related to a kind of super-fine zinc dust, nano concave earth, inorganic adhesive of adopting is nano concave earth inorganic zinc-rich protective system of making of main raw material and preparation method thereof.
Background technology
Corrosion of metal refers to that metal is subjected to the chemistry of surrounding medium or electrochemical action and destroyed phenomenon.Corrosion of metal spreads all over the national economy every field, has brought huge loss to national economy.The metal scrapped of annual whole world corrosion is approximately 100,000,000 tons according to statistics, accounts for 20%～40% of annual production.At present, the financial loss that causes because of the metal construction corrosion in whole world every year is up to more than hundreds billion of dollars.For a long time, people adopt multiple technologies that metal is protected always, prevent the generation of corroding.Wherein, one of effective, the most the most frequently used method of hardware protection against corrosion is at metallic surface coating protective system.
Zinc-rich paint has again electrochemical galvanic protection effect due to the shielding effect that both has physical property, thereby is widely used in the protection against corrosion of pipeline, bridge, vehicle, chemical industry equipment, boats and ships etc., is one of present the most widely used heavy-duty coating.According to the difference of filmogen, zinc-rich paint can be divided into organic zinc-rich paint and the large class of inorganic zinc coating two.Organic zinc-rich paint is take synthetic resins (as epoxy resin, poly-vinegar resin etc.) as filmogen, rust proof paint take the high-content zinc powder as color stuffing, owing to there being volatile organic matter (VOC) in organic zinc-rich paint, thereby it has larger negative impact to environment.Inorganic zinc coating be the aqueous solution take alkalimetal silicate as the film forming base fluid, and with the composite high-performance inorganic coating that forms of zinc powder.Compare organic zinc-rich paint, inorganic zinc coating environmental protection (VOC free), temperature tolerance are high, are one of environment-friendly type coatings of tool development prospect in the world at present.
Inorganic zinc coating has advantages of above-mentioned, but also comes with some shortcomings simultaneously: in the coating of inorganic zinc coating, zinc content surpasses more than 70%, and " crisp " impact resistance is not good for coating; Coating and basal body binding force are not high easy to crack, can produce the holiday of be full of cracks etc.These factors have affected Corrosion Protection and the comprehensive mechanical property of inorganic zinc coating, have limited the widespread use of this coating.
Publication number is that the Chinese invention patent application of CN101418150A discloses a kind of novel waterborne zinc-rich anti-corrosive paint, is comprised of first, second component, in this coating total weight percent, comprises: first component, zinc powder 50%～56%, thixotropic agent 10%～15%; The second component, potassium silicate 8%～10%, water 17%～20%, thickening material 1%～2% and auxiliary agent 4%～7%, during use, the mixing of first, second component gets waterborne zinc-rich anti-corrosive paint.Composite by said components improved the antiseptic property of coating, simultaneously, has sticking power, high thermal resistance and ageing resistance preferably, makes it have the long-effective corrosion effect.But the mechanical property of this waterborne zinc-rich anti-corrosive paint is not good, and is as all relatively poor in resistance to impact shock and snappiness, and its mechanical property remains further to be improved.
Summary of the invention
The invention provides a kind of nano concave earth inorganic zinc-rich protective system, composite by each component can significantly improve resistance to impact shock and the snappiness of nano concave earth inorganic zinc-rich protective system of the present invention.
A kind of nano concave earth inorganic zinc-rich protective system is mixed by first component and second component, and the mass ratio of first component and second component is 1:2～4;
In first constituent mass percentage ratio 100%, described first component is comprised of the component of following quality percentage composition;
Inorganic adhesive 68%～87%;
Synthetic resin emulsion 8%～30%;
Wetting dispersing agent 1.5%～4%;
Defoamer 0.5%～2%;
In second constituent mass percentage ratio 100%, described second component is comprised of the component of following quality percentage composition;
Zinc powder 85%～98%;
Nano concave earth 2%～15%.
In the present invention, nano concave earth used by recessed native ore powder through purify, Redispersion is prepared from, and is a kind of natural nanometer fibrous inorganic materials.The nano concave earth specific surface area is large, porosity is high, and surface atom has high nonsaturation, therefore the particle surface activity of nano concave earth is very large, by surface treatment and emulsify at a high speed dispersion treatment, can be uniformly dispersed in nano concave earth inorganic zinc-rich protective system of the present invention.In the paint solidification process, nano concave earth surface atom and inorganic adhesive reaction make coating curing form passive film.The recessed soil of fibrous nano that disperses can effectively be filled the pin hole of coating, suppresses the formation of coating be full of cracks.In addition, nano concave earth has filamentary structure can transmit the absorption of stress high-energy in coating, suppresses the generation of tiny crack in coating, thereby effectively resists surging force and control the crack.Therefore, the nano concave earth inorganic zinc-rich protective system at above-mentioned specific components and certain content composition has resistance to impact shock and snappiness preferably.
As preferably, the modulus of described inorganic adhesive is 3.0～5.0, the inorganic adhesive of this modulus has better film-forming properties and dry film sticking power, described inorganic adhesive is one or more in potassium silicate solution, sodium silicate solution, lithium silicate solution, multiple referring to can be adopted the commercially available prod at two or more (comprising two kinds).
Synthetic resin emulsion can improve the stable and dispersed of coating, as preferably, described synthetic resin emulsion is benzene emulsion or organosilicon crylic acid latex, the preferred inorganic adhesive of benzene emulsion or organosilicon crylic acid latex and the present invention has better consistency, can make nano concave earth inorganic zinc-rich protective system of the present invention have excellent stability and dispersed.
Wetting dispersing agent can improve the dispersion stabilization of solid particulate in coating, as preferably, described wetting dispersing agent is polycarboxylate sodium's type wetting dispersing agent, polycarboxylate sodium's type wetting dispersing agent has better dispersion effect to nano concave earth in the present invention and zinc powder, polycarboxylate sodium's type wetting dispersing agent can adopt the commercially available prod, and the model that specifically can adopt Nuo Puke company to produce is polycarboxylate sodium's type wetting dispersing agent of SN-5040.
The formation that defoamer can suppress bubble in the coating preparation process reduces the dry film pore, as preferably, described defoamer is polyethers defoamer or silica-type defoamer, the SN154 type silica-type defoamer that specifically can adopt SPG-10 type polyethers defoamer that Nantong Hong Feng industry auxiliary agent company limited produces or the auspicious specialization work of Hangzhou card company to produce, polyethers defoamer or silica-type defoamer are in nano concave earth inorganic zinc-rich protective system of the present invention, diffustivity and good penetrability have better defoaming effect.
Zinc powder realizes that by its electrochemical cathodic protection that has and certain physical property shielding it is to the preservative activity of protected matrix; as preferably; the granularity of described zinc powder is 300 order to 800 orders, and the nano concave earth inorganic zinc-rich protective system of the present invention for preparing with 300 order to 800 order zinc powders has the homogeneity of better filming.
Nano concave earth has filamentary structure can transmit the absorption of stress high-energy in coating, suppress the generation of tiny crack in coating, thereby effectively resist surging force and control the crack, as preferably, described nano concave earth is the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m, and the nano concave earth inorganic zinc-rich protective system of the present invention for preparing with diameter 25～80nm, long 0.5～3 fibrous attapulgite of μ m has more excellent Corrosion Protection and mechanical property.
The present invention also provides a kind of preparation method of nano concave earth inorganic zinc-rich protective system, and the preparation process controllability is good, easy handling, and production cost is lower, is easy to suitability for industrialized production.
A kind of preparation method of nano concave earth inorganic zinc-rich protective system comprises the following steps:
1) preparation of first component: inorganic adhesive, synthetic resin emulsion, wetting dispersing agent and defoamer are mixed, namely get the first component;
2) add the second component in the first component in the step 1), namely nano concave earth and zinc powder, obtain nano concave earth inorganic zinc-rich protective system after mixing.
Step 2) in, the preparation of described nano concave earth comprises: under the effect of the high speed shear power of 5000～7000 rev/mins, recessed soil is added to the water formation suspension, and add hydrochloric acid and Sodium hexametaphosphate 99, standing after ultra-sonic oscillation, the system for the treatment of obviously is divided into the closely knit beds of precipitation of top suspension and bottom, pour out top suspension, the solid after suction filtration separates makes nano concave earth through vacuum-drying.Wherein, in preparation process, adding hydrochloric acid and Sodium hexametaphosphate 99 is in order to activate and to disperse, and is for the abundant aquation of recessed soil is disperseed to the suspension ultra-sonic oscillation.
Step 2) in, add the second component in the first component in the step 1), be preferably first in the first component in the step 1) and add nano concave earth, 1000～3000 rev/mins of high-speed stirring emulsifications, then add zinc powder.First add nano concave earth, high-speed stirring emulsification, being conducive to nano concave earth is uniformly dispersed in coating, make nano concave earth can transmit better the absorption of stress high-energy, suppress the generation of tiny crack in coating, add afterwards zinc powder, zinc powder makes the nano concave earth inorganic zinc-rich protective system of final preparation have the homogeneity of better filming again.
Compared with prior art, advantage of the present invention is as follows:
One, nano concave earth inorganic zinc-rich protective system of the present invention, the first component is comprised of inorganic adhesive, synthetic resin emulsion, wetting dispersing agent and the defoamer of certain content, the second component is comprised of zinc powder and the nano concave earth of certain content, nano concave earth used is natural mineral, starting material wide material sources, low price, composite by each component can significantly improve resistance to impact shock and the snappiness of nano concave earth inorganic zinc-rich protective system of the present invention.The advantages such as nano concave earth inorganic zinc-rich protective system of the present invention has with the metal base bonding force strong, and salt spray resistance, impact resistance are good, it not only is suitable for heavy anticorrosion aspect, and can be used for the occasion very high to the coating mechanical property requirements.Nano concave earth inorganic zinc-rich protective system of the present invention can be widely used in the corrosionproof protections such as the oily platform of offshore drill quarrying, boats and ships, petrochemical equipment and coastal region bridge, pipeline, has good economic benefit and wide market outlook.
Two, nano concave earth inorganic zinc-rich protective system of the present invention can adopt spraying or brush, and the coating rate of drying is fast, and priming paint and other antifouling paste of filming as the metallic surface have fine matching capacity, for a long time salt spray resistance and damp and hot corrosion failure.
Three, the preparation method of nano concave earth inorganic zinc-rich protective system of the present invention, the preparation process controllability is good, easy handling, production cost is lower, is easy to large-scale industrialization production.
Description of drawings
Fig. 1 is the transmission electron microscope photo of nano concave earth of the present invention (being the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m).
Embodiment
By embodiment, the present invention is described in further detail.
A kind of preparation method of nano concave earth inorganic zinc-rich protective system comprises the following steps:
1) preparation of first component:
In first constituent mass percentage ratio 100%, the first component adopts the component of following quality percentage composition;
Inorganic adhesive 68%～87%;
Synthetic resin emulsion 8%～30%;
Wetting dispersing agent 1.5%～4%;
Defoamer 0.5%～2%;
Be that 3.0～5.0 inorganic adhesive (one or more in potassium silicate solution, sodium silicate solution, lithium silicate solution) is put into container with modulus, add above-mentioned synthetic resin emulsion (benzene emulsion or organosilicon crylic acid latex), wetting dispersing agent (polycarboxylate sodium's type wetting dispersing agent) and defoamer (polyethers defoamer or silica-type defoamer) to make the first component in stirring;
2) preparation of nano concave earth in the second component: recessed soil forms suspension in adding the 1000mL deionized water with 50g under the effect of high-speed stirring (6000 rev/mins), and add 2.5mol hydrochloric acid and 1.0mol Sodium hexametaphosphate 99, through ultra-sonic oscillation, the abundant aquation of recessed soil is disperseed, then standing three hours, the system for the treatment of obviously is divided into the closely knit beds of precipitation of top suspension and bottom, pour out top suspension, solid after suction filtration separates made above-mentioned nano concave earth in 12 hours in 60 ℃ of lower vacuum-dryings, be diameter 25～80nm, the fibrous attapulgite of long 0.5～3 μ m, the transmission electron microscope photo of this nano concave earth as shown in Figure 1.
3) preparation of nano concave earth inorganic zinc-rich protective system:
In second constituent mass percentage ratio 100%, the second component is comprised of the component of following quality percentage composition;
Zinc powder 85%～98%;
Nano concave earth 2%～15%.
With step 2) nano concave earth of preparation adds in oneself first component through preparing, by high speed (6000 rev/mins) emulsification, nano concave earth is uniformly dispersed in liquid, at last, add 300～800 order zinc powders, the mass ratio of first component and second component is 1:2～4, make both fully to mix evenly, namely get nano concave earth inorganic zinc-rich protective system.
Resistance to impact shock, salt fog resistance, snappiness and the sticking power of nano concave earth inorganic zinc-rich protective system of the present invention is respectively according to GB/T1732-1993, GB/T1771-1991, GB/T1731-1993, GB/T1720-1989 standard testing.
Embodiment 1
1) getting 87 gram moduluses is that (ocean, Xingtai chemical industry company limited produces for potassium silicate-sodium silicate solution of 3.5, model DY-KN), and add 10 gram benzene emulsions (ROHM AND HAAS AS-398), 2 gram wetting dispersing agents (model that Nuo Puke company produces is polycarboxylate sodium's type wetting dispersing agent of SN-5040) and 1 gram defoamer the SPG-10 type polyethers defoamer of production (the Nantong Hong Feng industry auxiliary agent company limited), stirring disperses it fully, makes the first component;
2) 8 gram nano concave earths (the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m) are added in above-mentioned first component solution, stirring under 1500 rev/mins of conditions was uniformly dispersed nano concave earth in 1.5 hours in liquid, add at last 292 gram 500 order zinc powders, the mass ratio of first component and second component is 1:3, and continue to stir 30 minutes, filter and obtain nano concave earth inorganic zinc-rich protective system.
The present embodiment nano concave earth inorganic zinc-rich protective system is sprayed onto respectively on the tinplate matrix that sand paper was processed and on the iron plate of sandblasting with the high pressure Air spraying.After solidifying fully, model Y1 must film.Give over to benchmark test.
Embodiment 2
1) getting 81 gram moduluses is that (ocean, Xingtai chemical industry company limited produces for 4.0 potassium silicate solution, model DY-K) and add 15 gram benzene emulsions (ROHM AND HAAS AS-398), 2.5 gram wetting dispersing agents (model that Nuo Puke company produces is polycarboxylate sodium's type wetting dispersing agent of SN-5040) and 1.5 gram defoamers the SPG-10 type polyethers defoamer of production (the Nantong Hong Feng industry auxiliary agent company limited), stirring disperses it fully, makes the first component.
2) 10 gram nano concave earths (the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m) are added in above-mentioned first component solution, stirring under 1500 rev/mins of conditions was uniformly dispersed nano concave earth in 1.5 hours in liquid, add at last 290 gram 600 order zinc powders, the mass ratio of first component and second component is 1:3, and continue to stir 30 minutes, filter and obtain nano concave earth inorganic zinc-rich protective system.
The present embodiment nano concave earth inorganic zinc-rich protective system is sprayed onto respectively on the tinplate matrix that sand paper was processed and on the iron plate of sandblasting with the high pressure Air spraying.After solidifying fully, model Y2 must film.Give over to benchmark test.
Embodiment 3
1) to get 86 gram moduluses be 4.8 lithium silicate solution (production of Zibo chemical reagent Co., Ltd., Factory) and add 8 gram benzene emulsions (ROHM AND HAAS AS-398), 4 gram wetting dispersing agents (model that Nuo Puke company produces is polycarboxylate sodium's type wetting dispersing agent of SN-5040) and the 2 gram defoamers SN154 type silica-type defoamer of production (the auspicious specialization work of Hangzhou card company), stirring disperses it fully, makes the first component.
2) 4 gram nano concave earths (the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m) are added in above-mentioned first component, stirring under 1500 rev/mins of conditions was uniformly dispersed nano concave earth in 1.5 hours in liquid, add at last 196 gram 400 order zinc powders, the mass ratio of first component and second component is 1:2, and continue to stir 30 minutes, filter and obtain nano concave earth inorganic zinc-rich protective system.
The present embodiment nano concave earth inorganic zinc-rich protective system is sprayed onto respectively on the tinplate matrix that sand paper was processed and on the iron plate of sandblasting with the high pressure Air spraying.After solidifying fully, model Y3 must film.Give over to benchmark test.
Embodiment 4
1) getting 68 gram moduluses is that (ocean, Xingtai chemical industry company limited produces for potassium silicate-sodium silicate solution of 3.0, model DY-KN) and add 30 gram organosilicon crylic acid latexs (east subfamily power BC-3206), 1.5 gram wetting dispersing agents (model that Nuo Puke company produces is polycarboxylate sodium's type wetting dispersing agent of SN-5040) and 0.5 gram defoamer the SN154 type silica-type defoamer of production (the auspicious specialization work of Hangzhou card company), stirring disperses it fully, makes the first component.
2) 30 gram nano concave earths (the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m) are added in above-mentioned first component solution, stirring under 1500 rev/mins of conditions was uniformly dispersed nano concave earth in 1.5 hours in liquid, add at last 170 gram 300 order zinc powders, the mass ratio of first component and second component is 1:2, and continue to stir 30 minutes, filter and obtain nano concave earth inorganic zinc-rich protective system.
The present embodiment nano concave earth inorganic zinc-rich protective system is sprayed onto respectively on the tinplate matrix that sand paper was processed and on the iron plate of sandblasting with the high pressure Air spraying.After solidifying fully, model Y4 must film.Give over to benchmark test.
Embodiment 5
1) to get 80 gram moduluses be lithium silicate-sodium silicate solution (production of Zibo chemical reagent Co., Ltd., Factory) of 3.0 and add 15 gram organosilicon crylic acid latexs (east subfamily power BC-3206), 3 gram wetting dispersing agents (model that Nuo Puke company produces is polycarboxylate sodium's type wetting dispersing agent of SN-5040) and the 2 gram defoamers SN154 type silica-type defoamer of production (the auspicious specialization work of Hangzhou card company), stirring disperses it fully, makes the first component.
2) 20 gram nano concave earths (the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m) are added in above-mentioned first component, stirring under 1500 rev/mins of conditions was uniformly dispersed nano concave earth in 1.5 hours in liquid, add at last 380 gram 800 order zinc powders, the mass ratio of first component and second component is 1:4, and continue to stir 30 minutes, filter and obtain nano concave earth inorganic zinc-rich protective system.
The present embodiment nano concave earth inorganic zinc-rich protective system is sprayed onto respectively on the tinplate matrix that sand paper was processed and on the iron plate of sandblasting with the high pressure Air spraying.After solidifying fully, model Y5 must film.Give over to benchmark test.
The rich zinc of table 1 is coated with lamina membranacea performance evaluation
As can be seen from the test results, nano concave earth inorganic zinc-rich protective system of the present invention has the sticking power close with conventional zinc-rich anti-corrosive paint, but its resistance to impact shock and snappiness are significantly improved, simultaneously, salt spray resistance also has lifting, it not only is suitable for heavy anticorrosion aspect, and can be used for the occasion very high to the coating mechanical property requirements.Conventional rich zinc is coated with lamina membranacea and refers to adopt the model of filming that obtains after commercially available inorganic zinc coating spraying, curing.
in existing zinc-rich anti-corrosive paint, some due to resistance to impact shock and snappiness not good, resistance to impact shock and snappiness are not carried out the sign of data, can't directly compare with nano concave earth inorganic zinc-rich protective system of the present invention, but some technical scheme also discloses resistance to impact shock and flexible characterization data, the Chinese invention patent application that is CN101445676A as publication number discloses a kind of high-efficient zinc-rich anti-corrosive paint and preparation thereof, the resistance to impact shock of its high-efficient zinc-rich anti-corrosive paint is 50kgcm(GB/T1732-1993), snappiness is 1mm(GB/T1731-1993), testing method is identical with the present invention, and the resistance to impact shock in nano concave earth inorganic zinc-rich protective system embodiment of the present invention is 110～125kgcm, than prior art, had very significantly and improved.
Claims (10)
1. a nano concave earth inorganic zinc-rich protective system, is characterized in that, mixed by first component and second component, and the mass ratio of first component and second component is 1:2～4;
In first constituent mass percentage ratio 100%, described first component is comprised of the component of following quality percentage composition;
Inorganic adhesive 68%～87%;
Synthetic resin emulsion 8%～30%;
Wetting dispersing agent 1.5%～4%;
Defoamer 0.5%～2%;
In second constituent mass percentage ratio 100%, described second component is comprised of the component of following quality percentage composition;
Zinc powder 85%～98%;
Nano concave earth 2%～15%.
2. nano concave earth inorganic zinc-rich protective system according to claim 1, is characterized in that, the modulus of described inorganic adhesive is 3.0～5.0.
3. nano concave earth inorganic zinc-rich protective system according to claim 1 and 2, is characterized in that, described inorganic adhesive is one or more in potassium silicate solution, sodium silicate solution, lithium silicate solution.
4. nano concave earth inorganic zinc-rich protective system according to claim 1, is characterized in that, described synthetic resin emulsion is benzene emulsion or organosilicon crylic acid latex.
5. nano concave earth inorganic zinc-rich protective system according to claim 1, is characterized in that, described wetting dispersing agent is polycarboxylate sodium's type wetting dispersing agent.
6. nano concave earth inorganic zinc-rich protective system according to claim 1, is characterized in that, described defoamer is polyethers defoamer or silica-type defoamer.
7. nano concave earth inorganic zinc-rich protective system according to claim 1, is characterized in that, the granularity of described zinc powder is 300 order to 800 orders.
8. nano concave earth inorganic zinc-rich protective system according to claim 1, is characterized in that, described nano concave earth is the fibrous attapulgite of diameter 25～80nm, long 0.5～3 μ m.
9. the preparation method of according to claim 1～8 described nano concave earth inorganic zinc-rich of any one protective systems, is characterized in that, comprises the following steps:
1) preparation of first component: inorganic adhesive, synthetic resin emulsion, wetting dispersing agent and defoamer are mixed, namely get the first component;
2) add the second component in the first component in the step 1), namely nano concave earth and zinc powder, obtain nano concave earth inorganic zinc-rich protective system after mixing.
10. the preparation method of nano concave earth inorganic zinc-rich protective system according to claim 9, it is characterized in that, step 2) in, the preparation of described nano concave earth comprises: under the effect of the high speed shear power of 5000～7000 rev/mins, recessed soil is added to the water formation suspension, and add hydrochloric acid and Sodium hexametaphosphate 99, standing after ultra-sonic oscillation, the system for the treatment of obviously is divided into the closely knit beds of precipitation of top suspension and bottom, pour out top suspension, the solid after suction filtration separates makes nano concave earth through vacuum-drying.
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| CN105273454A (en) * | 2014-07-15 | 2016-01-27 | 中国科学院宁波材料技术与工程研究所 | Nanometer inorganic zinc-rich composite anticorrosive coating and preparation method thereof |
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