CN103937369A - Environment-friendly anticorrosive coating material for automobile parts and preparation method thereof - Google Patents
Environment-friendly anticorrosive coating material for automobile parts and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly anticorrosive coating material for automobile parts and a preparation method thereof. The environment-friendly anticorrosive coating material comprises an ingredient A and an ingredient B, wherein the ingredient A comprises epoxy resin, pigment/filler, auxiliaries and an organic solvent, and the ingredient B comprises polyamide resin, a siloxane compound, a tertiary amine curing accelerator and an organic solvent. According to the anticorrosive coating material disclosed by the invention, the construction solid content is high (not lower than 60wt%), the VOC (Volatile Organic Compound) emission is low during construction, and the construction performance and film coating property are excellent; the coating material can be applied to anticorrosive coating layers of automobile metal parts, such as transmission cases, chassis parts, axles and other castings, the coating supporting is simple, the requirements on substrate pretreatment are low, sandblasting and phosphating treatment are not required, and good film coating performance can be guaranteed by only cleaning and degreasing; and the environment-friendly anticorrosive coating material for the automobile parts, disclosed by the invention, is simple in preparation process and is energy-saving and environment-friendly, and the prepared product is stable in performance.
Description
Technical field
The present invention relates to a kind of protective system, particularly a kind of environment-friendly type high solid protective system that is applicable to coating automobile parts and preparation method thereof.
Background technology
The metalwork blank of automobile component mostly is hot-rolled sheet and foundry goods, specifically comprises wheel box, chassis member, vehicle bridge and other foundry goods etc., before moulding or before application, adopts shot-peenings or sandblasting more, and acidic treatment is eliminated gradually.At the bottom of developed country, disk-like accessory application generally adopts phosphatization, ability cathode electrophoresis or powder coating process, and large assembly is generally that part line carries out assembling after electrophoresis or powder coating again, as required assembly is being sprayed to bottom surface or self-vulcanizing finish paint.China's coating automobile parts, because industrial scale is generally less, relatively backward generally, be mainly reflected in technique not high with the level of the aspects such as coated material of using.
Corrosion-resistant epoxy paint is widely used in the heavy corrosion-resistant field such as boats and ships, inner and outer walls of pipeline, mine steelframe, aircraft, bullet train.In order to obtain better anticorrosion ability, generally in coating, add containing chromium rust-stabilising pigment, as adopt zinc yellow, chrome yellow, strontium yellow, phosphorus zinc chromate etc. as rust-stabilising pigment, chromium metal is harmful, especially sexavalent chrome has carinogenicity, between the usage period after preparation, construction and the film forming of coating, workmen and environment are caused to serious harm.For this reason, develop successively the protective system of some Chrome-frees both at home and abroad, CN101260252A as open in Chinese patent application discloses a kind of chromium-free Dyclo paint, usings flake zinc powder and aluminium powder as rust-stabilising pigment.In addition on the one hand, since the nineties in 20th century, countries in the world start the feature of environmental protection of car paint to require more and more higher.The < < solvent steering order that Europe proposes for 1994---painting dressing automobiles process emission limit set > > has just clearly stipulated that coaling production line for cars organic solvent emission amount (comprising priming paint, middle japanning, finish paint application) must not be higher than 45g/m
2; Germany is more strict to the emission request of volatile organic matter, and emission standard must not be higher than 35g/m
2.Therefore, develop a kind of construction admittedly containing heavy metals such as high, VOC discharge is relatively low, not leaded, chromium, the protective system that is suitable for automobile component (rolling plate and foundry goods class) application is significant.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly type high solid protective system that is applicable to coating automobile parts and preparation method thereof.
The technical solution used in the present invention is:
A kind of environmentally friendly car parts protective system, comprise A component and B component, wherein, A component comprises the organic solvent of epoxy resin 20～40wt%, color stuffing 30～60wt%, auxiliary agent 2～6wt% and surplus, and B component comprises the organic solvent of polyamide resin 40～60wt%, silicone compounds 2～10wt%, tertiary amines curing catalyst 1～5wt% and surplus.
Preferably, the weight ratio of A component and B component is 3～6:1.
Preferably, described epoxy resin is epoxy resin I and the epoxy resin II of weight ratio 4～40:1, and wherein, the epoxy equivalent (weight) of epoxy resin I is 0～1000, and the epoxy equivalent (weight) of epoxy resin II is 1000～5000.
Preferably, described silicone compounds is at least one in original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid four butyl esters and oligomer thereof, vinyltriethoxysilane, γ-(glycidoxy) propyl-triethoxysilicane, γ aminopropyltriethoxy silane, N-amino-ethyl-3-aminopropyl triethoxysilane, r-chloropropyl trimethoxyl silane, hexamethyldisiloxane, hexamethyldisilazane, tetramethyl divinyl siloxanes, hydroxyl-terminated injecting two methyl siloxane.
Preferred, described silicone compounds is γ aminopropyltriethoxy silane and/or N-amino-ethyl-3-aminopropyl triethoxysilane.
Preferably, described tertiary amines curing catalyst is at least one in DMP-10, DMP-20, DMP-30, benzyldimethylamine, glyoxal ethyline, 2-ethyl-4-methylimidazole.
Preferably, described color stuffing is the mixture of tinting pigment, pigment extender and rust-stabilising pigment.
Preferably, described auxiliary agent comprises defoamer, flow agent, dispersion agent, anti-sagging agent.
Preferably, described anti-sagging agent is organobentonite and/or aerosil.
The preparation method of protective system for environmentally friendly car parts, comprises the following steps:
1) formulation components A:
The epoxy resin of formula ratio 60～80wt%, dispersion agent, defoamer are mixed, add again anti-sagging agent and color stuffing, mix, 500～1000rpm stirs lower after pre-dispersed 30～60 minutes, joins in sand mill, be ground to fineness≤15 μ m, filter, add remaining epoxy resin, flow agent and solvent, stir, filter, obtain component A;
2) preparation part B:
By formula ratio, successively polyamide resin, silicone compounds, promotor and solvent are added in container, 300～600rpm stirs 30～60 minutes, filters, and obtains component B;
3) before use, by proportioning, A component and B component are mixed, obtain environmentally friendly car parts protective system;
The formula of described protective system as mentioned above.
The invention has the beneficial effects as follows:
Protective system of the present invention construction solid content high (>=60 wt%), during construction VOC discharge low, there is excellent workability, paint film property.This coating can be used for comprising the corrosion protection coating of the automobile metal type components such as wheel box, chassis member, vehicle bridge and other foundry goods, coating is supporting simple, pre-treatment requirement to ground is low, without sandblast ball blast and bonderizing, only needs cleaning and degreasing can guarantee good paint film property.
Environmentally friendly car parts of the present invention is simple by the preparation technology of protective system, energy-conserving and environment-protective, and the product performance of preparation are stable.
Embodiment
A kind of environmentally friendly car parts protective system, comprise A component and B component, wherein, A component comprises the organic solvent of epoxy resin 20～40wt%, color stuffing 30～60wt%, auxiliary agent 2～6wt% and surplus, and B component comprises the organic solvent of polyamide resin 40～60wt%, silicone compounds 2～10wt%, tertiary amines curing catalyst 1～5wt% and surplus.
Preferably, the weight ratio of A component and B component is 3～6:1.
Preferably, described epoxy resin is epoxy resin I and the epoxy resin II of weight ratio 4～40:1, wherein, the epoxy equivalent (weight) of epoxy resin I is 0～1000, preferred, the epoxy equivalent (weight) of epoxy resin I is 200～800, the available commercialization trade mark has the DER671 of DOW Chemical, DER662, DER664, DER640, the Epikote834 of shell chemistry, Epikote220, Epikote1001, Epikote1002, the R140 of Mitsui Chemicals, R144, the Epiclon860 of DIC, Epiclon1050, Epiclon2055, Epiclon3050, Epiclon4050 etc., the epoxy equivalent (weight) of epoxy resin II is 1000～5000, preferred, the epoxy equivalent (weight) of epoxy resin II is 2000～4000, the available commercialization trade mark has DER667, DER668, the DER669 of DOW Chemical, the Epikote1007 of shell chemistry, Epikote1009, Epikote2009, the R307 of Mitsui Chemicals, R309, the Epiclon7050 of DIC, Epiclon9055 etc.
Preferably, described silicone compounds is at least one in original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid four butyl esters and oligomer thereof, vinyltriethoxysilane, γ-(glycidoxy) propyl-triethoxysilicane, γ aminopropyltriethoxy silane, N-amino-ethyl-3-aminopropyl triethoxysilane, r-chloropropyl trimethoxyl silane, hexamethyldisiloxane, hexamethyldisilazane, tetramethyl divinyl siloxanes, hydroxyl-terminated injecting two methyl siloxane.Preferred, described silicone compounds is γ aminopropyltriethoxy silane and/or N-amino-ethyl-3-aminopropyl triethoxysilane.
Preferably, described tertiary amines curing catalyst is at least one in DMP-10, DMP-20, DMP-30, benzyldimethylamine, glyoxal ethyline, 2-ethyl-4-methylimidazole.
Preferably, organic solvent is at least one in alcohol, aromatic hydrocarbon, ketone, alcohol ether, ester.Preferred, be dimethylbenzene and/or butanols.
Preferably, described color stuffing is the mixture of tinting pigment, pigment extender and rust-stabilising pigment.Preferably, described tinting pigment be that titanium dioxide, carbon black, phthalocyanine blue, phthalocyanine green, iron oxide black, red iron oxide, iron oxide yellow, permanent bordeaux, quinacridone are red, at least one in permanent violet; Described pigment extender is at least one in process white, calcium carbonate, talcum powder, kaolin; Described rust-stabilising pigment is at least one in aluminium triphosphate, zinc phosphate, modified zinc phosphate, superfine calcium phosphate, calcium iron powder, barium metaborate.
Preferably, described auxiliary agent comprises defoamer, flow agent, dispersion agent, anti-sagging agent.
Preferably, described anti-sagging agent is organobentonite and/or aerosil.
The preparation method of protective system for environmentally friendly car parts, comprises the following steps:
1) formulation components A:
The epoxy resin of formula ratio 60～80wt%, dispersion agent, defoamer are mixed, add again anti-sagging agent and color stuffing, mix, 500～1000rpm stirs lower after pre-dispersed 30～60 minutes, joins in sand mill, be ground to fineness≤15 μ m, filter, add remaining epoxy resin, flow agent and solvent, stir, filter, obtain component A;
2) preparation part B:
By formula ratio, successively polyamide resin, silicone compounds, promotor and solvent are added in container, 300～600rpm stirs 30～60 minutes, filters, and obtains component B;
3) before use, by proportioning, A component and B component are mixed, obtain environmentally friendly car parts protective system;
The formula of described protective system as mentioned above.
Preferably, step 1) adds epoxy resin in two batches before and after grinding, and on the basis that guarantees dispersive ability, reduces amount of grinding, improves mill efficiency, meanwhile, after being convenient to grind, residual mill base in equipment cavity is ejected.
Below in conjunction with specific embodiment to the preferred embodiment of the invention with and the useful technique effect that produced further explain, but, it will be appreciated by those skilled in the art that the present invention is not limited to the content of these concrete embodiments and embodiment.In an embodiment, unless separately there is clear and definite indication, " part " refers to " weight part ", " ratio " refers to " weight ratio ", and " % " refers to " weight percent ".
embodiment 1
An environmentally friendly car parts protective system, comprises A component host and B component curing agents, and A component formula is as follows:
Weight of material per-cent/%
DER671 24.0，
DER667 2.0，
Dispersant B YK ANTI-TERRA-U 2.0,
Organobentonite 0.5,
Aerosil 0.5,
Carbon black 2.5,
Zinc phosphate 10.5,
Aluminium triphosphate 8.5,
Process white 23.0,
Defoamer BYK-054 0.3,
Flow agent BYK-358 N 0.5,
Dimethylbenzene 18,
Butanols 7.7.
B component formula is as follows:
Weight of material per-cent/%
Polyamide resin (amine value 155) 46.0,
DMP-30 3.0，
Aminopropyl triethoxysilane 3.0,
Dimethylbenzene 38.0,
Butanols 10.0.
The preparation technology of coating is as follows:
1) formulation components A
First master grind: 14.6 parts of epoxy resin DER671,1 part of epoxy resin DER667, dispersion agent, defoamer are mixed, after adding again organobentonite, aerosil and the color stuffing of sag prevention to stir, 1000rpm stirs after pre-dispersed 30 minutes, join in sand mill, be ground to fineness≤15 μ m, filter, standby; Ground mill base is added to paint mixing tank, add remaining epoxy resin DER671, DER667 in component A, flow agent and mixed solvent, stir, and filters, packs and to obtain component A;
2) formulation components B
By formula ratio, successively each composition of B component is added in container, 600rpm stirs 30 minutes, filters and packages and obtains B component;
3) before use, A component and B component are mixed according to the weight ratio of 4:1, obtain protective system.
embodiment 2
An environmentally friendly car parts protective system, comprises A component and B component, and A component formula is as follows:
Weight of material per-cent/%
Epikote834 22.0，
Epikote1009 5.0，
Dispersion agent DISPERBYK-110 2.0,
Organobentonite 0.5,
Aerosil 0.5,
Carbon black 2.5,
Rutile type Titanium Dioxide 15.0,
Zinc phosphate 10.5,
Aluminium triphosphate 8.5,
Process white 10.0,
Defoamer BYK-052 0.3,
Flow agent BYK-320 0.5,
Dimethylbenzene 16,
Butanols 6.7.
B component formula is as follows:
Weight of material per-cent/%
Polyamide resin (amine value 180) 46.0,
Altax P-30 1.0,
N-amino-ethyl-aminopropyl triethoxysilane 4.0,
Dimethylbenzene 38.0,
Butanols 11.0.
The preparation technology of coating is as follows:
1) formulation components A
First master grind: 17 parts of epoxy resin Epikote834,2 parts of epoxy resin Epikote1009, dispersion agent, defoamers are mixed, after adding again organobentonite, aerosil and the color stuffing of sag prevention to stir, 1000rpm stirs after pre-dispersed 30 minutes, join in sand mill, be ground to fineness≤15um, filter, standby; Ground mill base is added to paint mixing tank, add remaining epoxy resin Epikote834, Epikote1009 in component A, flow agent and mixed solvent, stir, and filters, packs and to obtain component A;
2) formulation components B
By formula ratio, successively each composition of B component is added in container, 300rpm stirs 1 hour, filters and packages and obtains B component;
3) before use, A component and B component are mixed according to the weight ratio of 5:1, obtain protective system.
embodiment 3
An environmentally friendly car parts protective system, comprises A component and B component, and A component formula is as follows:
Weight of material per-cent/%
R140 32.0，
R307 1.0，
Dispersion agent DISPERBYK-142 2.0,
Organobentonite 0.5,
Aerosil 0.5,
Carbon black 1.0,
Rutile type Titanium Dioxide 15.0,
Permanent bordeaux 0.5,
Phthalocyanine blue 0.5,
Zinc phosphate 10.5,
Aluminium triphosphate 8.5,
Process white 5.0,
Defoamer Surfynol 104E 0.3,
Flow agent BYK-320 0.5,
Dimethylbenzene 15.5,
Butanols 6.7.
B component formula is as follows:
Weight of material per-cent/%
Polyamide resin (amine value 120) 50.0,
Promotor dimethyl benzylamine 3.0,
N-octyl Trimethoxy silane 7.0,
Dimethylbenzene 30.0,
Butanols 10.0.
The preparation technology of coating is as follows:
1) formulation components A
First master grind: 23 parts of epoxy resin R140,1 part of epoxy resin R307, dispersion agent, defoamer are mixed, after adding again organobentonite, aerosil and the color stuffing of sag prevention to stir, 1000rpm stirs after pre-dispersed 30 minutes, join in sand mill, be ground to fineness≤15 μ m, filter, standby; Ground mill base is added to paint mixing tank, add remaining epoxy resin R140 in component A, flow agent and mixed solvent, stir, and filters, packs and to obtain component A;
2) formulation components B
By formula ratio, successively each composition of B component is added in container, 600rpm stirs 30 minutes, filters and packages and obtains B component;
3) before use, A component and B component are mixed according to the weight ratio of 6:1, obtain protective system.
embodiment 4
An environmentally friendly car parts protective system, comprises A component and B component, and A component formula is as follows:
Weight of material per-cent/%
Epiclon860 18.0，
Epiclon7050 2.0，
Dispersion agent DISPERBYK-142 1.0,
Organobentonite 0.3,
Aerosil 0.3,
Carbon black 2.0,
Rutile type Titanium Dioxide 38.5,
Permanent bordeaux 1.5,
Phthalocyanine blue 1.5,
Aluminium triphosphate 10.5,
Process white 6.0,
Defoamer Surfynol 104E 0.2,
The WE-D811 of flow agent Cigna 0.2,
Dimethylbenzene 10,
Butanols 8.
B component formula is as follows:
Weight of material per-cent/%
Polyamide resin (amine value 120) 60.0,
Promotor dimethyl benzylamine 5.0,
N-octyl Trimethoxy silane 10.0,
Dimethylbenzene 18.0,
Butanols 7.0.
The preparation technology of coating is as follows:
1) formulation components A
First master grind: 15 parts of epoxy resin Epiclon860,1 part of epoxy resin Epiclon7050, dispersion agent, defoamer are mixed, after adding again organobentonite, aerosil and the color stuffing of sag prevention to stir, 1000rpm stirs after pre-dispersed 30 minutes, join in sand mill, be ground to fineness≤15 μ m, filter, standby; Ground mill base is added to paint mixing tank, add remaining epoxy resin Epiclon860, Epiclon7050 in component A, flow agent and mixed solvent, stir, and filters, packs and to obtain component A;
2) formulation components B
By formula ratio, successively each composition of B component is added in container, 600rpm stirs 30 minutes, filters and packages and obtains B component;
3) before use, A component and B component are mixed according to the weight ratio of 3:1, obtain protective system.
embodiment 5
An environmentally friendly car parts protective system, comprises A component and B component, and A component formula is as follows:
Weight of material per-cent/%
DER640 38.0，
Epikote2009 2.0，
Dispersion agent DISPERBYK-142 2.5,
Organobentonite 1.5,
Aerosil 0.3,
Carbon black 1.5,
Rutile type Titanium Dioxide 9.0,
Zinc phosphate 8.0,
Aluminium triphosphate 4.5,
Process white 7.0,
Defoamer BYK-054 0.9,
The WE-D811 of flow agent Cigna 0.8,
Dimethylbenzene 14,
Butanols 10.
B component formula is as follows:
Weight of material per-cent/%
Polyamide resin (amine value 120) 40.0,
Promotor dimethyl benzylamine 2.0,
N-octyl Trimethoxy silane 2.0,
Dimethylbenzene 40.0,
Butanols 16.0.
The preparation technology of coating is as follows:
1) formulation components A
First master grind: 30 parts of epoxy resin DER640,2 parts of epoxy resin Epikote2009, dispersion agent, defoamers are mixed, after adding again organobentonite, aerosil and the color stuffing of sag prevention to stir, 800rpm stirs after pre-dispersed 40 minutes, join in sand mill, be ground to fineness≤15 μ m, filter, standby; Ground mill base is added to paint mixing tank, add remaining epoxy resin DER640 in component A, flow agent and mixed solvent, stir, and filters, packs and to obtain component A;
2) formulation components B
By formula ratio, successively each composition of B component is added in container, 500rpm stirs 30 minutes, filters and packages and obtains B component;
3) before use, A component and B component are mixed according to the weight ratio of 6:1, obtain protective system.
comparative example
An environmentally friendly car parts protective system, comprises A component and B component, and A component formula is as follows:
Weight of material per-cent/%
Epikote834 22.0，
Epikote1009 5.0，
Dispersion agent DISPERBYK-110 2.0,
Organobentonite 0.5,
Aerosil 0.5,
Carbon black 2.5,
Rutile type Titanium Dioxide 15.0,
Zinc phosphate 10.5,
Aluminium triphosphate 8.5,
Process white 10.0,
Defoamer BYK-052 0.3,
Aminopropyl triethoxysilane 3.0,
Flow agent BYK-320 0.5,
Dimethylbenzene 13,
Butanols 6.7.
B component formula is as follows:
Weight of material per-cent/%
Polyamide resin (amine value 180) 46.0,
Altax P-30 3.0,
Dimethylbenzene 40.0,
Butanols 11.0.
The preparation technology of coating, with embodiment 2, mixes A component and B component according to the weight ratio of 5:1, obtain protective system.
The protective system that adopts embodiment 1～3 and comparative example 1 preparation, is used conventional aerial spraying to prepare model, and ground is cold-rolled steel sheet, and cleaning by degreasing is anticorrosion with painting coating after drying.According to national standard method, the performance of formed paint film is detected, result is as follows:
As seen from the above table, comparative example is directly added to coupling agent silicone compounds in A component host, because coupling agent has higher reactive behavior, operability is not good, cause A component tackify even to have the phenomenon of gel on the one hand, cause on the other hand the consumption of coupling agent must be controlled at smaller category, otherwise easier gel.The present invention joins silicone compounds in B component curing agents, well to have solved the problems referred to above.
Protective system of the present invention construction solid content high (>=60 wt%), during construction VOC discharge low, there is excellent workability, paint film property.This coating requires low to the pre-treatment of ground, without sandblast ball blast and bonderizing, only need cleaning and degreasing can guarantee good paint film property.
Claims (10)
1. an environmentally friendly car parts protective system, comprise A component and B component, wherein, A component comprises the organic solvent of epoxy resin 20～40wt%, color stuffing 30～60wt%, auxiliary agent 2～6wt% and surplus, and B component comprises the organic solvent of polyamide resin 40～60wt%, silicone compounds 2～10wt%, tertiary amines curing catalyst 1～5wt% and surplus.
2. protective system according to claim 1, is characterized in that: the weight ratio of A component and B component is 3～6:1.
3. protective system according to claim 1, it is characterized in that: described epoxy resin is epoxy resin I and the epoxy resin II of weight ratio 4～40:1, wherein, the epoxy equivalent (weight) of epoxy resin I is 0～1000, and the epoxy equivalent (weight) of epoxy resin II is 1000～5000.
4. protective system according to claim 1, is characterized in that: described silicone compounds is at least one in original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid four butyl esters and oligomer thereof, vinyltriethoxysilane, γ-(glycidoxy) propyl-triethoxysilicane, γ aminopropyltriethoxy silane, N-amino-ethyl-3-aminopropyl triethoxysilane, r-chloropropyl trimethoxyl silane, hexamethyldisiloxane, hexamethyldisilazane, tetramethyl divinyl siloxanes, hydroxyl-terminated injecting two methyl siloxane.
5. protective system according to claim 4, is characterized in that: described silicone compounds is γ aminopropyltriethoxy silane and/or N-amino-ethyl-3-aminopropyl triethoxysilane.
6. protective system according to claim 1, is characterized in that: described tertiary amines curing catalyst is at least one in DMP-10, DMP-20, DMP-30, benzyldimethylamine, glyoxal ethyline, 2-ethyl-4-methylimidazole.
7. protective system according to claim 1, is characterized in that: described color stuffing is the mixture of tinting pigment, pigment extender and rust-stabilising pigment.
8. protective system according to claim 1, is characterized in that: described auxiliary agent comprises defoamer, flow agent, dispersion agent, anti-sagging agent.
9. protective system according to claim 8, is characterized in that: described anti-sagging agent is organobentonite and/or aerosil.
10. the preparation method of protective system for environmentally friendly car parts, comprises the following steps:
1) formulation components A:
The epoxy resin of formula ratio 60～80wt%, dispersion agent, defoamer are mixed, add again anti-sagging agent and color stuffing, mix, 500～1000rpm stirs lower after pre-dispersed 30～60 minutes, joins in sand mill, be ground to fineness≤15 μ m, filter, add remaining epoxy resin, flow agent and solvent, stir, filter, obtain component A;
2) preparation part B:
By formula ratio, successively polyamide resin, silicone compounds, promotor and solvent are added in container, 300～600rpm stirs 30～60 minutes, filters, and obtains component B;
3) before use, by proportioning, A component and B component are mixed, obtain environmentally friendly car parts protective system;
The formula of described protective system is as described in claim 1～9 any one.
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| CN110760916B (en) * | 2019-11-18 | 2022-04-05 | 和县科嘉阀门铸造有限公司 | Method for improving corrosion resistance of magnesium alloy valve |
| CN111471372A (en) * | 2020-05-15 | 2020-07-31 | 晋江市中德顺钢结构件工程发展有限公司 | Corrosion-resistant counterweight block casting and manufacturing method thereof |
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