CN114316799B - Multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation - Google Patents
Multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation Download PDFInfo
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Abstract
The invention provides a multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation, which comprises at least one material group, wherein each group comprises an aqueous base material, an anti-settling agent and surface-passivated binary metal nano-micron sheet powder, the binary metals in the groups are binary alloys consisting of two different metals, at least one metal in the binary alloys in each group in a plurality of material groups is different from the metal types in the binary alloys in all other groups, and a coating formed by the material provided by the invention realizes a multi-layer coating layer with low thickness, ultra-long protection time, environment friendliness and excellent binding force, and the highest salt spray test protection time reaches 3500 h.
Description
Technical Field
The invention relates to an environment-friendly antirust material, in particular to a multi-metal water-based low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation, and a coating formed by the same, belonging to the field of environment-friendly antirust materials.
Background
The rust-proof capability of steel parts in the vehicle industry, such as fasteners, balance arms, door locks and other stamping parts, is improved year by year along with the improvement of the quality of automobiles. The time from 200 hours of galvanization to 480 hours to 840 hours of the normal zinc-aluminum alloy coating.
The materials required by the middle-high-end rust prevention of the current vehicle iron parts in China completely depend on the import of Japan, Europe and America. The imported rust-proof material is a solvent-type zinc-aluminum material except that the imported rust-proof material of the Japan system is water-based, and the United states system of Germany and the United states system are all solvent-type zinc-aluminum materials.
The imported solvent type zinc-aluminum material contains 20% -30% of high-irritation-taste solvents such as xylene and PMA, is a standard non-environment-friendly solvent with low VOC solvent, and belongs to a flammable solvent. The metallic water-based zinc-aluminum material of the Japanese system still contains high VOC. Except the defects of solvent and VOC, the cost of imported zinc-aluminum antirust materials is high, and the cost of antirust treatment is above 4.5RMB/KG when 720 hours of antirust treatment is required in neutral salt spray.
The water-based zinc-aluminum antirust material technology was invented by the foreigners in the 90 s and introduced into China from Japan, and the VOC is still high, but the requirement of neutral salt spray for more than 840 hours of secondary coating is difficult to meet all the time. For example, chinese patent document CN108192403A discloses a solvent-based zinc-aluminum coating, which is prepared from component a and component B in a mass ratio of 4: 1-5: 1, mixing; the component A comprises the following components in parts by weight: 75-90 parts of zinc-aluminum alloy powder, 15-18 parts of organic solvent, 3-12 parts of filler, 0.2-0.7 part of coupling agent and 0.3-0.9 part of anti-settling agent; the component B is tetraethoxysilane hydrolysate; the anti-settling auxiliary agent is a mixture of MoS2 and isocyanate group terminated hyperbranched polyurethane, and the mass ratio of MoS2 to isocyanate group terminated hyperbranched polyurethane is 5-9: 1. for example, chinese patent document CN203427394U discloses a chromium-free zinc-aluminum coating composite coating structure on a carbon steel substrate, which comprises a carbon steel substrate, a chromium-free zinc-aluminum coating, a water-based sealing surface coating and a solvent sealing surface coating, wherein the chromium-free zinc-aluminum coating is disposed on the upper surface of the carbon steel substrate, the water-based sealing surface coating is disposed on the upper surface of the chromium-free zinc-aluminum coating, and the solvent sealing surface coating is disposed on the upper surface of the water-based sealing surface coating. For example, chinese patent CN102504700A discloses a water-based chromium-free zinc-aluminum paint and a preparation method thereof, which comprises an agent a and an agent B which are mixed and mixed evenly when in use, wherein the total weight of the agent a and the agent B is 100%, and the agent a comprises the following components in percentage by weight: emulsifier: 1% -5%, alcohol: 10% -25%, defoamer: 0% -5%, thickener: 0% -0.3%, metal zinc aluminum powder or zinc aluminum paste: 25% -35%; the agent B comprises the following components in percentage by weight: deionized water: 20% -40%, silane coupling agent: 10 to 20 percent. However, in the prior art, the zinc-aluminum coating is firstly oxidized by zinc, aluminum and air in the air through the oxidation potential difference of the zinc-aluminum metal and the iron substrate, and the iron material part is not oxidized into rust (Fe2O3) by oxygen in the air until the zinc-aluminum coating is completely consumed. Xylene and PMA solvents belong to toxic and hazardous substances, not only can cause health influence on field operators, but also can possibly burn the solvents. Although the aqueous zinc-aluminum coating of the japanese system solves the problem of the solvent, it still has the disadvantages of a certain volatile solvent and a high material cost.
With the trend of increasing the requirement for rust prevention of parts, the neutral salt spray test standard has been increased from 480 hours to 720 hours by the system automobile factories in europe and america on the day. Taking standard parts and stamping parts for vehicles as examples, the standard of 720 hours of red rust is generally reached, and the European and American system needs to be coated with 3 coats to ensure the effect. When the rust-proof standard of 1000 hours red rust is required, the European and American solvent type rust-proof material needs to be coated by 4, and the daily water-based rust-proof material needs to be coated by 3 to meet the requirement. Due to the requirement of the reserved size of the fastener, if the antirust coating is larger than 15 micrometers (15 micrometers), the bolt/nut can be plugged because the antirust coating is too thick, and the requirement of a general rule (marking) cannot be met. All the existing low-film-thickness (10-30 mu m) zinc-aluminum antirust material technologies generally have the problems of environmental protection, high treatment cost, low cost performance, difficult quality improvement and the like.
Disclosure of Invention
In view of the above problems, the present invention provides a multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material and coating based on surface passivation, which overcomes or at least partially solves the above problems. The invention uses the passivation principle to passivate the surface of the multielement metal nano-micron sheet powder (the grain diameter is 15-18 microns, and the thickness is 0.2-0.4 microns) with extremely high activity, so that the active superfine multielement metal nano-micron sheet powder can be stabilized in water. Besides, the multi-metal nano-micron flake powder can be stabilized in water, and the overall electrochemical protection effect of the multi-metal nano-micron flake powder coating cannot be reduced due to the isolation of the multi-metal nano-micron flake powder. The surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material and the coating provided by the invention also reduce the potential difference between the coating and an iron material, slow down the oxidation speed of the coating, and improve the antirust capability of the coating, and the neutral salt spray test can reach 3000-3500 hours in an average 12 micron.
According to one aspect of the invention, the surface passivation-based multi-metal water-based low-film-thickness environment-friendly high-salt spray antirust material comprises at least one material group, wherein each material group comprises a water-based base material, an anti-settling agent and surface passivation binary metal nano-micron flake powder, the binary metals in the material groups are binary alloys formed by two different metals, and at least one metal in the binary alloys in each material group is different from the metal species in all other groups of the binary alloys.
Optionally, the number of said material groups is 1-2, preferably 2.
Preferably, the aqueous base material includes an aqueous silane coupling agent, and the anti-settling agent includes nanoscale silica.
Preferably, the binary metal comprises any one of zinc aluminum, zinc magnesium, zinc tin, or a combination thereof.
The preparation method of the surface-passivated binary metal nano-micron sheet powder comprises the steps of firstly preparing the binary metal nano-micron sheet powder and then passivating the surface of the prepared binary metal nano-micron sheet powder.
Preferably, the preparation method of the binary metal nano-micron sheet powder is a deposition coating method.
Preferably, the passivation comprises surface coating passivation of the binary metal nano-micron sheet powder by using an aqueous coupling agent.
Optionally, the aqueous coupling agent comprises a modified silane, preferably the aqueous coupling agent comprises octyl triethoxysilane (C) 10 H 20 O 5 Si), phenyltrimethylsilane (C) 11 H 22 O 4 Si)。
Preferably, the particle size of the binary metal nano-micron sheet powder is 15-18 microns, and the thickness of the binary metal nano-micron sheet powder is 0.2-0.4 micron.
Preferably, each of the at least one material groups further comprises a water molecule blocker, preferably MHH-NH 1000.
The surface passivation treatment of the invention prevents the zinc-aluminum micro-sheet metal powder from reacting with water in water to generate hydrogen and metal hydroxide, reduces the oxidation potential difference (less than 0.32mV) of binary alloy and iron parts, achieves the stability of the material in water, retards the oxidation speed of the alloy, and achieves the neutral salt measurement performance at a lower coating film thickness (9-12 mu m) through a slower oxidation speed, namely 1500-3500 hours.
According to another aspect of the invention, a coating formed by the surface passivation based multi-metal aqueous low-film-thickness environment-friendly high-salt spray antirust material comprises at least one coating layer, the at least one coating layer is laminated in a direction away from the surface of a coated material, and the difference of oxidation potential of the laminated layer in the direction is gradually increased.
It will be appreciated that when there is only one coating layer, the oxidation potential difference increases from no presence to a non-zero value in the direction away from the surface of the coated material.
Preferably, the coating is sequentially formed by three coating layers of surface-passivated zinc aluminum, surface-passivated zinc magnesium and surface-passivated zinc tin in the direction in a stacking mode.
Preferably, the total thickness of the coating layers is 11-13 μm, and the number of coating layers forming each coating layer is 2-3.
The surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material and coating provided by the invention have the following beneficial effects:
1. using non-silicon dioxide (SiO) 2 ) The passivation way of wrapping the binary alloy micro powder can stabilize the nano-micro tablet powder in water without influencing the conductivity of metal, and the water-based antirust material can keep stable for a long time without deterioration;
2. the excellent rust-proof capability of the iron parts is improved from 480-1000 hours of the prior zinc-aluminum coating to 1500-3500 hours;
3. the thickness of the coating film required by high antirust capacity is reduced, and the thickness of the zinc-aluminum coating material is reduced to 9-12 μm from 18-30 μm in 1500 hours;
4. the processing procedures of the antirust coating are reduced, for example, at 1500 hours, the existing imported zinc-aluminum coating needs 4-5 coatings to be reduced to 2 coatings (only 3 coatings are needed for multiple layers, but the protective capability can be improved to 3500 hours); the material cost and the energy consumption are reduced, and the productivity and the output value are improved;
5. the coating has excellent binding force, does not fall off powder after being collided, and the film thickness is not damaged due to the production process, thereby providing long-term stable antirust protection capability;
6. the coating has high hardness and is resistant to collision, a stable friction coefficient of parts is provided, and the tightness of the fastener and the combination quality and efficiency of an assembly line are ensured;
7. the protection period of the iron material is prolonged, the neutral salt spray test is performed for 100 hours, which is equivalent to the outdoor antirust protection capability for one year, and the protection period is increased from 500-1000 hours (5-10 years of antirust) of the existing import to 1500-3500 hours (15-35 years of antirust);
8, water-based environmental protection, no pungent smell, low VOC (less than 25mg/L) and no combustion;
9. the increased specific surface area of the nanoscale flaky powder can be replaced by a larger water-blocking area.
The surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt-mist antirust material disclosed by the invention has aqueous environment-friendly and zero-volatility organic chemical components (VOC is 0), neutral salt mist for more than 1500 hours can be provided for an antirust coating with the thickness of 10-12 micrometers, and a neutral salt mist test is carried out on the film thickness of 11-13 micrometers reaching 3500 hours. In the field of low-film-thickness rust prevention of vehicle steel parts, the coating surpasses the current industrial standard, fills the technical vacancy of high-end low-film-thickness rust-preventing coating of the current domestic vehicle steel parts such as fasteners, balance arms, chassis parts, door locks and other stamping parts, and is a new industrial standard and a high industrial standard for low-film-thickness rust prevention of iron materials of vehicle industrial parts.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram showing binary flaky rust inhibitive material micro powders each passivated according to an embodiment of the present invention;
FIG. 2 is a schematic diagram showing a three-layer coating structure on the surface of a ferrous material according to an embodiment of the present invention;
wherein the reference numeral 1-a coating layer formed of material a, 2-a coating layer formed of material B, and 3-a coating layer formed of material C.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the invention are shown in the drawings, it should be understood that the invention can be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The embodiment of the invention provides a surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt spray antirust material, which comprises at least one material group, wherein each material group can comprise an aqueous base material, an anti-settling agent and surface passivation binary metal nano-micron flake powder, the binary metals in the group are binary alloys formed by two different metals, and at least one metal in the binary alloys in each group in a plurality of material groups is different from the metal types in the binary alloys in all other groups.
In the surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt mist antirust material provided by the embodiment, a passivation approach of wrapping binary alloy micro powder with non-silicon dioxide (SiO2) is adopted, so that the conductivity of metal is not influenced, the nano-micro tablet powder is stabilized in water, and the surface of the highly active multi-metal nano-micro tablet powder (with the particle size of 15-18 micrometers and the thickness of 0.2-0.4 micrometer) is passivated by utilizing a passivation principle, so that the active fine multi-metal nano-micro tablet powder can be stabilized in water, and the aqueous antirust material is kept stable for a long time and is not deteriorated. Optionally, the number of material groups is 1-2, preferably 2.
The multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation in the embodiment can comprise at least one material group, and for each material group in the at least one material group, the multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material can comprise an aqueous base material, an anti-settling agent and surface-passivated binary metal nano-micro flake powder. The aqueous base may include, among other things, an aqueous silane coupling agent.
The anti-settling agent may comprise nanoscale silica. The nano-scale silicon dioxide is more referred to as nano-silicon dioxide.
The material set provided by this embodiment further includes binary metal nano-micron flake powder with surface passivation, where the binary metal may include any one of zinc aluminum, zinc magnesium, and zinc tin, or a combination of at least two of them. The preparation method of the surface-passivated binary metal nano-micron flake powder can comprise the following steps: firstly, binary metal nano-micron flake powder is prepared, and then the surface of the binary metal nano-micron flake powder is passivated, so that the active fine multi-element metal nano-micron flake powder can be stabilized in water, and further the surface passivated binary metal nano-micron flake powder is obtained. In an optional embodiment of the present invention, a deposition coating method may be adopted to prepare the binary metal nano-micron sheet powder, wherein the particle size of the binary metal nano-micron sheet powder is preferably 15-18 microns, and the thickness is 0.2-0.4 microns. When the prepared binary metal nano-micron sheet powder is passivated, the surface of the binary metal nano-micron sheet powder can be wrapped and passivated by using an aqueous coupling agent.
The water-based coupling agent adopted in the embodiment of the invention for passivating the surface coating of the binary metal nano-micron sheet powder can comprise modified silane. Alternatively, the aqueous coupling agent comprises octyl triethoxysilane (C) 10 H 20 O 5 Si), phenyltrimethylsilane (C) 11 H 22 O 4 Si)。
As introduced above, the multi-metal water-based low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation of the embodiment of the invention comprises at least one material group, and optionally, each material group in the at least one material group can also comprise a water molecule blocking and changing agent. The water molecule resisting and changing agent has the function of preventing the metal microchip powder from reacting with water, thereby improving the stability of the water-based antirust coating in water. The water molecule blocking agent of the present embodiment is preferably MHH-NH 1000.
The embodiment of the invention also provides a coating formed by the multielement metal water-based low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation, wherein the coating comprises at least one coating layer, the at least one coating layer is laminated in the direction far away from the surface of the coated material, and the oxidation potential difference of the laminated layer is gradually increased in the direction. It will be appreciated that when there is only one coating layer, the oxidation potential difference increases from no presence to a non-zero value in the direction away from the surface of the coated material. Preferably, the coating is sequentially formed by three coating layers of surface-passivated zinc aluminum, surface-passivated zinc magnesium and surface-passivated zinc tin in the direction in a stacking mode. Preferably, the total thickness of the coating is 11-13 μm.
The coating that is formed by the low membrane thickness environmental protection high salt fog antirust material of many metals waterborne based on surface passivation that this embodiment provided, the cohesion is superior, collide with and do not fall whitewashed, the membrane thickness is not impaired because of manufacturing process, can provide long-term stable rust-resistant protective capability, and, the coating hardness that this embodiment provided is high, resistant colliding with, provide the stable coefficient of friction of part, can ensure the tightness and the assembly line combination quality and the efficiency of fastener, thereby solve among the prior art antirust material technique ubiquitous environmental protection, the treatment cost is high, the low, the quality is difficult to promote the scheduling problem.
The multi-metal water-based low-film-thickness environment-friendly high-salt-spray antirust material and coating based on surface passivation described above are explained in detail by using a plurality of specific examples.
Example 1
The embodiment provides a surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material A, which comprises 30-40 parts by mass of an aqueous silane coupling agent, 30-40 parts by mass of surface passivation Zn-Al nano-micron flake powder (the particle size is 15-18 microns, the thickness is 0.2-0.4 microns), 1-5 parts by mass of MHH-NH1000 and 15-35 parts by mass of pure water.
Example 2
The embodiment provides a surface passivation-based multi-metal aqueous low-film-thickness environment-friendly high-salt-spray antirust material B, which comprises 20-30 parts by mass of an aqueous silane coupling agent, 30-35 parts by mass of zinc sheet micro powder, 8-12 parts by mass of surface passivation Zn-Sn nano-micron sheet powder (with the particle size of 15-18 microns and the thickness of 0.2-0.4 microns), 1-5 parts by mass of MHH-NH1000 and 10-15 parts by mass of pure water.
Example 3
This example is three sets of materials AB of examples 1-2, that is, the materials in this example may include two sets of materials, which correspond to material a of example 1 and material B of example 2. FIG. 1 shows schematic diagrams of binary flaky rust inhibitive material micro powders each passivated according to an embodiment of the present invention.
This example utilized the two sets AB of example 3 to form three laminated coatings 1-3 on the surface of the fe-based material as schematically shown in figure 2. Wherein, the coating layers 1-3 are respectively formed by the material AB, so that the whole laminated coating layer can be completed by 3 coating, and the antirust protection capability is shown in the table 1 compared with the prior Japanese water-based anticorrosive material. Referring to fig. 2, the oxidation potential of the iron substrate (i.e., iron-based material) is about 0.44mv, the oxidation potential of the first layer of the anti-rust coating close to the iron-based material is less than or equal to 0.76mv, the oxidation potential of the second layer of the anti-rust coating is less than or equal to 0.9mv, and the oxidation potential of the third layer of the anti-rust coating is less than or equal to 1.1 mv.
TABLE 1 comparison of inventive examples with Japanese Water-based materials
| Coating number | Thickness (μm) | Salt spray test time (h) | |
| Aqueous Japanese material | 2 | 8-10 | 720 |
| Japanese water-based material | 3 | 11-13 | Not more than 1500 |
| Example 1 | 2 | 9-11 | Greater than 1500 |
| Example 2 | 2 | 11-13 | Greater than 2000 |
| Example 3 | 3 | 11-13 | 3000-3500 |
By comparing the material in the embodiment with the Japanese water-based material, under the scene that the coating number is the same and the thickness is similar, the salt spray testing time of the material provided by the embodiment of the invention is obviously longer than that of the Japanese water-based material. In particular, the coating corresponding to the embodiment 3 of the invention has the coating number of 3 and the thickness of 12 μm, and the corresponding salt spray test time is 3000-3500 hours. That is, after the coating formed by the material provided by the embodiment of the invention is coated on the iron-based material, the coating can be increased from 500-.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments can be modified or some or all of the technical features can be equivalently replaced within the spirit and principle of the present invention; such modifications or substitutions do not depart from the scope of the present invention.
Claims (1)
1. The coating formed by the multielement metal water-based low-film-thickness environment-friendly high-salt-spray antirust material based on surface passivation is characterized in that the coating is sequentially laminated into three coating layers, namely a first antirust coating layer, a second antirust coating layer and a third antirust coating layer, in the direction away from the surface of the coated material, and the oxidation potential difference of the laminated layers is gradually increased in the direction; the total thickness of the coating is 11-13 mu m, and the coating number of each coating layer is 2-3;
the multi-metal water-based low-film-thickness environment-friendly high-salt mist antirust material based on surface passivation comprises a plurality of material groups, wherein each group comprises a water-based base material, an anti-settling agent, surface-passivated binary metal nano-micron flake powder and a water molecule heat-transfer inhibitor MHH-NH1000, the binary metals in the groups are binary alloys formed by two different metals, and at least one metal in the binary alloys in each group in the plurality of material groups is different from the metal species in the binary alloys in all other groups;
the surface-passivated binary metal nano-micron sheet powder in the first antirust coating layer is surface-passivated zinc aluminum nano-micron sheet powder, the surface-passivated binary metal nano-micron sheet powder in the second antirust coating layer is surface-passivated zinc magnesium nano-micron sheet powder, and the surface-passivated binary metal nano-micron sheet powder in the third antirust coating layer is surface-passivated zinc tin nano-micron sheet powder;
the aqueous base material comprises an aqueous silane coupling agent, and the anti-settling agent comprises nanoscale silica;
the preparation method of the surface-passivated binary metal nano-micron sheet powder comprises the steps of firstly preparing the binary metal nano-micron sheet powder, and then passivating the surface of the prepared binary metal nano-micron sheet powder; the particle size of the binary metal nano-micron sheet powder is 15-18 microns, and the thickness of the binary metal nano-micron sheet powder is 0.2-0.4 micron;
the passivation comprises the steps of coating and passivating the surface of the binary metal nano-micron sheet powder by using an aqueous coupling agent; the aqueous coupling agent includes octyl triethoxysilane.
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