WO2018210212A1 - Ductile iron pipe having anti-corrosion inner coating, and production process therefor - Google Patents

Ductile iron pipe having anti-corrosion inner coating, and production process therefor Download PDF

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Publication number
WO2018210212A1
WO2018210212A1 PCT/CN2018/086787 CN2018086787W WO2018210212A1 WO 2018210212 A1 WO2018210212 A1 WO 2018210212A1 CN 2018086787 W CN2018086787 W CN 2018086787W WO 2018210212 A1 WO2018210212 A1 WO 2018210212A1
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WIPO (PCT)
Prior art keywords
coating
epoxy
epoxy resin
ductile iron
iron pipe
Prior art date
Application number
PCT/CN2018/086787
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French (fr)
Chinese (zh)
Inventor
李成章
何奇书
李军
李宁
申勇
岳江峰
贾清波
王颖
王志强
申艳英
马宗勇
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新兴河北工程技术有限公司
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Publication of WO2018210212A1 publication Critical patent/WO2018210212A1/en

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04Coatings characterised by the materials used
    • F16L58/14Coatings characterised by the materials used by ceramic or vitreous materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04Coatings characterised by the materials used
    • F16L58/10Coatings characterised by the materials used by rubber or plastics
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04Coatings characterised by the materials used
    • F16L58/10Coatings characterised by the materials used by rubber or plastics
    • F16L58/1009Coatings characterised by the materials used by rubber or plastics the coating being placed inside the pipe
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the technical field of ductile iron pipes, in particular to a ductile iron pipe for a high performance epoxy ceramic anticorrosive inner coating applied to a water pipeline.
  • Ductile iron pipe has the advantages of good mechanical properties, high interface reliability, good corrosion resistance and long service life. It is widely used in urban construction water and gas transmission industries.
  • the existing standard internal anti-corrosion coating is cement mortar lining.
  • the inner lining has the advantages of good economy and active anti-corrosion.
  • the pH value of water quality will rise in the initial stage of water delivery.
  • the corrosive soft water is also highly corrosive to this inner coating.
  • the main problem is that the surface treatment and environmental humidity of the substrate are very high, otherwise it may cause defects such as foaming of the coating.
  • the ductile iron pipe is especially hot-casting.
  • the caliber ductile iron pipe the inherent inner surface slag pit and crack are very difficult to meet the surface treatment requirements, so it is particularly likely to cause problems such as foaming and peeling of the polyurethane inner coating.
  • Epoxy coatings are widely used in the protection of steel, but their performance requirements vary according to their application.
  • special areas such as high temperature areas in the Middle East
  • higher requirements are placed on the high temperature resistance of epoxy anticorrosive linings to ensure coating adhesion and coating performance during stacking in high temperature areas like the Middle East.
  • the technical problem to be solved by the invention is to provide a ductile iron pipe with an anti-corrosion inner coating and a production process thereof, and the epoxy resin coating layer of the invention is coated on the inner wall of the ductile iron pipe to have excellent high temperature resistance and corrosion resistance.
  • Sexual, wear-resistant, smooth surface can reduce the frictional resistance between water and pipe wall, thus ensuring the long service life of the pipeline.
  • a ductile iron pipe with an anti-corrosion coating comprising a ductile iron pipe body, the two ends of which are a socket and a socket, and the inner wall of the ductile iron pipe is coated with the epoxy ceramic coating layer of the invention.
  • the commonly used phenolic epoxy coating layers are both solvent-based and solvent-free. Since the epoxy group of the novolac type epoxy resin is substantially ⁇ 2 and has a relatively high viscosity, it is usually prepared as a solvent-based paint, and the solvent-based phenolic epoxy paint has a common disadvantage of a general solvent-based paint, that is, it cannot be thick. Coating, the thickness of a single coating is about ⁇ 200 ⁇ m, and in the process of solvent evaporation, there will be more channels in the coating. These two disadvantages will seriously affect the corrosion resistance of the coating. Even a century of ductile iron pipes can not achieve the long-term anti-corrosion effect of demand. If a thick coating of heavy anti-corrosion effect is to be achieved, multi-pass coating must be used, and batch production of ductile iron pipes cannot be realized.
  • phenolic epoxy coating known as "solvent free”. Because of the high viscosity of the general polyfunctional phenolic epoxy resin, a relatively large amount of benzyl alcohol (a non-reactive diluent, which is retained in the coating due to its high boiling point) is usually added to such a coating. But these so-called solvent-free phenolic epoxy coatings are not really solvent-free. Some standards stipulate that a coating that achieves a mass solids content of ⁇ 95% is defined as a solvent-free coating, ie a small amount of benzyl alcohol or a solvent is added.
  • the solvent-free phenolic epoxy ceramic coating of the present invention achieves true solvent-free addition, thereby achieving a mass solid content of ⁇ 98%, even reaching a level of ⁇ 99%.
  • the solventless phenolic epoxy ceramic coating of the present invention is a two component epoxy coating of an epoxy resin component (component A) and an amine curing agent component (component B), wherein the epoxy resin component contains phenolic acid.
  • the epoxy resin, the epoxy equivalent of the novolac epoxy resin used is 160-190, and the content (parts by weight) of the novolac epoxy resin in the epoxy resin component is 20% to 60%. It has been found that the solvent-free phenolic epoxy ceramic coating of the invention can significantly improve the crosslinking density of the coating, improve the Tg of the coating, make the coating have high temperature resistance, and have excellent corrosion resistance, compared with the previous The coating layer improves the corrosion resistance and high temperature resistance of the pipe.
  • the current common ceramic powder is one or more of titanium dioxide, talc (mainly composed of magnesium silicate), calcium carbonate and silica.
  • titanium dioxide is generally used as a pigment
  • talcum powder The main role is to reduce the stress shrinkage of the coating; while calcium carbonate as a filler has better hiding power, which can reduce the cost of the coating; silica can reduce the internal stress of the coating and prevent cracking.
  • the prior art uses ceramic powder to have no requirement for the purity of the material, and the amount used is in the range of 0.2-30% of the total coating weight, and the amount used is small.
  • the present invention finds through experiments that although the phenolic epoxy coating without adding ceramic powder has greatly improved the performance of the coating itself, it was found that when the ceramic powder used is quartz powder or / and ⁇ -Al 2 O 3 , Is the ⁇ -Al 2 O 3 purity mass percentage ⁇ 98%, the quartz powder SiO 2 purity mass percentage ⁇ 99%, especially the high-purity aluminum oxide (ie corundum), the coating is extremely high Wear resistance.
  • These ceramic powders are not often used in the coatings industry, although some coatings use aluminum oxide, but they are all made of low-purity bauxite, which has a low content of aluminum oxide and is not wear-resistant like corundum. Sex.
  • the volume of ceramic powder used is between 20% and 40% of the coating volume (between 40% and 55% of the coating weight).
  • the coating has excellent wear resistance and can also significantly reduce the curing process of solvent-free coatings. Stress contraction. This is because when the amount of ceramic powder is small ( ⁇ 20% coating volume, that is, the weight of ceramic powder is about ⁇ 40% coating weight), the wear resistance of the coating cannot be guaranteed; when the amount of ceramic powder is large, the coating volume is exceeded. 40% of the base material does not wrap the pigment and filler well, the permeability of the coating increases, and the viscosity of the coating rises sharply. Therefore, although the solventless phenolic epoxy coating of the present invention does not achieve good results even with the coating process equipment of the present invention.
  • the ceramic powder used in the present invention is different from the commonly used pipe coating ceramic powder in that it can improve the pulverization of talc powder; avoid the reaction of calcium carbonate with other substances (such as acidic substances), and is intolerant.
  • the erosion of strong corrosive media can affect the acid resistance and water resistance of the coating in the coating.
  • the coating of the present invention can increase the amount of use to achieve better wear resistance and reduce the internal stress of the coating.
  • the thickness of the steel pipe coating is about 400 ⁇ m.
  • Anti-corrosion coatings extend the corrosion protection time.
  • the use of cathodic protection increases the operating cost of the pipeline.
  • the coating provided by the present invention has excellent wear resistance due to the volume of the ceramic powder used being between 20% and 40% of the coating volume (between 40% and 55% of the coating weight).
  • the stress shrinkage of the solventless coating curing process is remarkably reduced to achieve a coating thickness of ⁇ 500 ⁇ m, preferably 500 ⁇ m to 2000 ⁇ m, more preferably 1000 ⁇ m to 1500 ⁇ m.
  • the thickness of the coating has a close correlation with the anti-corrosion performance of the coating. The thicker the coating, the better the corrosion resistance.
  • the coating used for the high performance epoxy ceramic coating layer is a solventless phenolic epoxy ceramic coating.
  • the present invention provides a ductile iron pipe having an anticorrosive inner coating layer coated with an epoxy coating layer on the inner wall of the ductile iron pipe, and the coating used is a solventless phenolic epoxy coating, preferably solvent free Phenolic epoxy ceramic coating.
  • the high-performance epoxy ceramic coating layer has a volume solid content of ⁇ 98%, preferably ⁇ 99%.
  • the coating for the high performance epoxy ceramic coating layer is a solventless phenolic epoxy ceramic coating, wherein the ceramic powder as a filler has a volume of 20%-40 of the coating volume. %, preferably 20% to 30%.
  • the coating for the high performance epoxy ceramic coating layer is a solventless phenolic epoxy ceramic coating, wherein the ceramic powder as a filler is quartz powder or/and ⁇ -Al 2 O 3 , the ⁇ -Al 2 O 3 purity mass percentage ⁇ 98%; the quartz powder SiO 2 purity mass percentage ⁇ 99%.
  • the solventless phenolic epoxy ceramic coating used in the high performance epoxy ceramic coating layer is a two component coating, wherein one component is an epoxy resin component, one group Divided into an amine curing agent component, and the ratio of the epoxy resin component (A component) to the amine curing agent component (B component) is 1:1 (weight ratio).
  • the solventless phenolic epoxy ceramic coating used in the high performance epoxy ceramic coating layer is a two component epoxy coating, wherein the epoxy resin component contains phenolic epoxy
  • the epoxy resin component contains phenolic epoxy
  • the epoxy equivalent of the novolac epoxy resin used is 160-190
  • the content (parts by weight) of the novolac epoxy resin in the epoxy resin component is 20% to 60%.
  • the epoxy resin component (component A) of the high performance phenolic epoxy ceramic coating comprises:
  • Phenolic epoxy resin 20-60%
  • Liquid bisphenol A epoxy resin 0-25%
  • Ceramic powder 20-34%.
  • the auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent.
  • the phenolic epoxy resin has a phenolic epoxy resin having an epoxy equivalent of 160-190.
  • the phenolic epoxy resin has high functionality, increases the crosslink density of the coating, improves the Tg of the coating, imparts high temperature resistance to the coating, and excellent corrosion resistance, especially acid resistance.
  • the epoxy equivalent of the bisphenol A epoxy resin is 190 liquid epoxy resin, such as DER 331.
  • the reactive diluent is a glycidyl ether reactive reactive diluent having an epoxy equivalent of 175-330.
  • the reactive diluent has strong dilution ability to the solventless epoxy resin, can effectively reduce the viscosity of the system, and can increase the system.
  • the flexibility increases the impact resistance of the coating while avoiding the toxicity due to the use of inert diluents.
  • Commonly used commercial products are: polypropylene glycol diglycidyl ether, such as DER 732 of DOW, o-tolyl glycidyl ether, such as HELOXY 62.
  • the present invention incorporates suitable pigments depending on the particular application.
  • the rutile titanium dioxide R-930 and carbon black which are harmless to the human body are selected, and they may be used alone or in combination according to the color requirements of the coating film.
  • the ceramic powder is quartz powder or/and ⁇ -Al 2 O 3 .
  • the amine curing agent component (component B) comprises:
  • Amine curing agent 22-30%;
  • Ceramic powder 65-75%
  • the amine curing agent is a specially prepared modified amine curing agent, which can be Mannich base or/and modified alicyclic amine, Mannich base has low temperature curability, and has excellent adhesion to wet surfaces, It has good compatibility with the resin; alicyclic amine can increase the Tg of the coating, thereby improving the heat resistance and high temperature adhesion of the coating.
  • the catalyst is a tertiary amine catalyst such as Ancamine K54.
  • the auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent.
  • the ceramic powder is quartz powder or/and ⁇ -Al 2 O 3 .
  • the coating procedure of the high performance epoxy coating layer is as follows:
  • a and B components need to be preheated to 45-55 ° C;
  • a two-component spraying device respectively conveying the epoxy resin component and the curing agent component to the nozzle, and driving the spray cup to rotate at a high speed by a motor or an air motor to atomize and spray the coating onto the pipe;
  • Curing The coated ductile iron pipe needs to be heated and accelerated in the drying room.
  • the curing conditions are: curing temperature is 50-90 ° C, curing for more than 1 h; preferred curing conditions are: temperature is 75-85 ° C , curing for 2h; then curing at room temperature for 7d, ready to use.
  • the anti-corrosion coating provided by the invention is a high-performance phenolic epoxy ceramic coating layer sprayed on the inner wall of the ductile iron pipe.
  • the coating has excellent adhesion to the ductile iron pipe, and the tensile strength is tested by ASTM D4541, and the room temperature is tested. Pulling adhesion can reach more than 15Mpa, and high-temperature drawing adhesion (80°C) can reach more than 4Mpa.
  • the high-performance phenolic epoxy ceramic coating provided by the present invention can achieve a film thickness of 2000 ⁇ m at one time because it does not contain a solvent.
  • This coating is given by the addition of quartz powder or / and ⁇ -Al 2 O 3 ceramic powder filler, and its volume content accounts for more than 20% of the total volume of the coating, giving the coating excellent wear resistance according to ASTM D4060 Test, using CS-17 wheel, load 1kg, 1000 rpm, wear amount ⁇ 50mg.
  • the high performance phenolic epoxy ceramic inner anticorrosive coated ductile iron pipe provided by the invention has smooth inner wall, can effectively reduce the frictional resistance between the water medium and the pipe wall, and saves transportation energy.
  • the high performance phenolic epoxy ceramic inner anticorrosive coating provided by the invention is based on a phenolic epoxy film-forming material, has a high epoxy content, increases the crosslink density of the coating, and improves the Tg of the coating.
  • the coating has high temperature resistance, and the coating provided by the present invention can be used for long-term transportation of an aqueous medium of 80 °C.
  • the high-performance phenolic epoxy ceramic inner anticorrosive coating provided by the invention also has a phenolic epoxy-based film-forming substance, which increases the cross-linking density of the coating, and is excellent in the coating due to the addition of the ceramic powder.
  • the corrosion resistance ensures the 100-year life of ductile iron pipes.
  • the high performance phenolic epoxy ceramic coating provided by the invention does not contain any organic solvent, is safe, environmentally friendly and hygienic, and is tested by domestic and foreign authorities to meet the safety of GB 17219/T drinking water distribution equipment and protective materials. The evaluation criteria require that it be used for the delivery of drinking water.
  • the ductile iron pipe of the epoxy ceramic coating anticorrosive inner coating applied to the water pipeline is prepared as follows.
  • the preparation method comprises the following steps:
  • High-performance phenolic epoxy ceramic coatings have high viscosity at room temperature and must be preheated: components A and B must be preheated to 45-55 ° C to reduce viscosity;
  • the A component (epoxy resin component) and the B component (curing agent component) are separately delivered to the nozzle, and the spray cup is rotated at a high speed by a motor or an air motor to mix the coating mist. Sprayed onto a rotating tube;
  • (9) Curing After spraying, the ductile iron pipe needs to be heated in the drying room to accelerate the curing.
  • the curing conditions are: curing temperature is 50-90 ° C, curing for more than 1 h, and then curing at room temperature for 7 d; the preferred curing conditions are: temperature is Curing at 75-85 ° C for 2 h, then curing at room temperature for 7 d, ready for use.
  • the manufacturing process of the high performance phenolic epoxy ceramic coating is as follows:
  • Component A epoxy resin component, including novolac epoxy resin, or a mixture of phenolic epoxy resin and liquid bisphenol A epoxy resin, reactive diluent, auxiliary agent, pigment, ceramic powder.
  • relevant additives including wetting and dispersing agent, defoaming agent
  • Component B an amine curing agent component, including a Mannich base amine curing agent, a ceramic powder, an auxiliary agent; or a modified alicyclic amine curing agent, a ceramic powder, and an auxiliary agent.
  • amine curing agent component including a Mannich base amine curing agent, a ceramic powder, an auxiliary agent; or a modified alicyclic amine curing agent, a ceramic powder, and an auxiliary agent.
  • the ceramic powder is dispersed at a high speed to the desired fineness, and then the remaining auxiliary materials and the like are uniformly dispersed in a medium speed, and the package is filtered.
  • the coating materials given below were prepared and coated according to the method of the Preparation Examples, and the effects were compared after coating.
  • a coating material different from the coating material given by the present invention is prepared according to a method similar to the present invention according to a conventional technique in the art.
  • Comparative Example 1 is a "solvent-type coating"
  • Comparative Example 2 is a solventless coating currently conventionally used. It can be seen that the solvent-based coating is inferior to the solvent-free coating material in terms of coating process, acid resistance, distillation resistance, and abrasion resistance and high temperature resistance.
  • the "solvent-free coating” currently used in Comparative Example 2 although improving some properties of the solvent-based coating, still contains an undesired inactive diluent on the one hand, but is resistant to acid and water. Sexual aspects as well as wear resistance and high temperature resistance are still unsatisfactory.
  • the solventless coating of the present invention overcomes the dissatisfaction of the prior coatings and greatly improves the wear resistance, corrosion resistance, and particularly high temperature adhesion.
  • Comparative Examples 3 and 4 used a coating which is conventionally used in the prior art for ceramic powder.
  • the conventionally used ceramic powder has a large inconvenience in the process of preparation, and the existing ceramic powder calcium carbonate is easily reacted with other substances (for example, an acidic substance), and is not resistant to the corrosion of a highly corrosive medium in the coating. It will affect the acid resistance and water resistance of the coating; the talc powder and calcium carbonate have lower hardness than the high-purity ceramic powder material required by the present invention, and thus are significantly weaker in mechanical properties and chemical resistance than the coating used in the present invention.
  • the coating material of the present invention can meet the current needs of use, and has excellent corrosion resistance, wear resistance and high temperature resistance.
  • the ductile iron pipe with anticorrosive inner coating of the invention and the production process thereof have great influence in the field of water transportation and gas transmission.
  • the anti-corrosion coating provided by the invention is a high-performance phenolic epoxy ceramic coating layer sprayed on the inner wall of the ductile iron pipe, the coating has excellent adhesion to the ductile iron pipe, and the tensile strength test is tested by ASTM D4541, and the normal temperature drawing is performed.
  • the adhesion can reach more than 15Mpa, and the high-temperature drawing adhesion (80°C) can reach more than 4Mpa.
  • the ductile iron pipe with anti-corrosion inner coating of the invention and the production process thereof have strong industrial applicability and operability, and are of great significance for pipeline transportation.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Protection Of Pipes Against Damage, Friction, And Corrosion (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

A ductile iron pipe having an anti-corrosion inner coating, and a production process therefor. An epoxy coating is applied on the inner wall of the ductile iron pipe and the paint of the epoxy coating is a solvent-free phenolic epoxy ceramic paint. The volume solid content of the solvent-free phenolic epoxy ceramic paint is greater than or equal to 98%, preferably greater than or equal to 99%. By applying the epoxy ceramic coating to the inner wall of the ductile iron pipe, the ductile iron pipe is endowed with excellent high temperature resistance, anti-corrosion performance, and abrasive resistance, the surface is smooth, frictional resistance between water and the pipe wall can be reduced, and thus a long service life of the pipe can be ensured.

Description

具有防腐内涂层的球墨铸铁管及其生产工艺Ductile iron pipe with anti-corrosion inner coating and production process thereof 技术领域Technical field
本发明涉及球墨铸铁管技术领域,特别涉及一种应用于输水管道的高性能环氧陶瓷防腐内涂层的球墨铸铁管。The invention relates to the technical field of ductile iron pipes, in particular to a ductile iron pipe for a high performance epoxy ceramic anticorrosive inner coating applied to a water pipeline.
背景技术Background technique
球墨铸铁管具有力学性能好、接口可靠性高、耐腐蚀性能好、使用寿命长等优点,目前被广泛用于城建输水及输气等工业领域。现有的标准内防腐涂层为水泥砂浆内衬,此内衬具有经济性好、主动防腐的效果,但是由于水泥砂浆固有的碱性特征,在输水初期会引起水质的pH值升高,另外腐蚀性较大的软水也会对此种内涂层具有较强的腐蚀性。Ductile iron pipe has the advantages of good mechanical properties, high interface reliability, good corrosion resistance and long service life. It is widely used in urban construction water and gas transmission industries. The existing standard internal anti-corrosion coating is cement mortar lining. The inner lining has the advantages of good economy and active anti-corrosion. However, due to the inherent alkaline characteristics of cement mortar, the pH value of water quality will rise in the initial stage of water delivery. In addition, the corrosive soft water is also highly corrosive to this inner coating.
基于此原因球墨铸铁管行业也开发了其它有机内防腐涂层,例如聚氨酯涂层以及环氧涂层。For this reason, the ductile iron pipe industry has also developed other organic internal anti-corrosion coatings, such as polyurethane coatings and epoxy coatings.
对于聚氨酯涂层来说,存在的主要问题是对基材的表面处理及环境湿度要求很高,否则容易引起涂层起泡等缺陷,对于离心铸造成型的球墨铸铁管尤其是热模法铸造大口径球墨铸铁管来说,固有的内表面渣坑、龟裂,要达到表面处理要求是非常困难的,因此特别容易引起聚氨酯内涂层的起泡、剥落等问题。For polyurethane coatings, the main problem is that the surface treatment and environmental humidity of the substrate are very high, otherwise it may cause defects such as foaming of the coating. For centrifugal casting, the ductile iron pipe is especially hot-casting. For the caliber ductile iron pipe, the inherent inner surface slag pit and crack are very difficult to meet the surface treatment requirements, so it is particularly likely to cause problems such as foaming and peeling of the polyurethane inner coating.
环氧涂料被广泛应用于钢铁的防护,但均按照其应用领域不同对其性能要求也不同。对于球墨铸铁管来说,其主要用于埋地管线,作为市政、水利、海水淡化等领域的给水排水,要求使用年限达100年之久,尤其是软水、市政污水等腐蚀性强的水,这就要求环氧防腐内衬具有优异的防腐性、耐磨性,一般的溶剂型环氧涂料和无溶剂型涂料很难达到这样的要求。尤其对于特殊地区(例如中东高温地区),对环氧防腐内衬耐高温性能提出了更高要求,以保证在类似中东的高温地区堆放过程中涂层的附着力和涂层性能。Epoxy coatings are widely used in the protection of steel, but their performance requirements vary according to their application. For ductile iron pipe, it is mainly used for buried pipelines. As a water supply and drainage in the fields of municipal, water conservancy and seawater desalination, it requires a service life of 100 years, especially soft water such as soft water and municipal sewage. This requires an epoxy anticorrosive lining to have excellent corrosion resistance and wear resistance, and it is difficult to achieve such a requirement in general solvent-based epoxy coatings and solvent-free coatings. Especially for special areas (such as high temperature areas in the Middle East), higher requirements are placed on the high temperature resistance of epoxy anticorrosive linings to ensure coating adhesion and coating performance during stacking in high temperature areas like the Middle East.
但目前的环氧涂层还不能满足更高要求的防腐性和耐磨性的要求。因此研发一种耐高温性能,具有优异防腐性、耐磨性的高性能环氧陶瓷防腐涂层,是在高温环境下,输送腐蚀性水用球墨铸铁管内防腐涂层研究的重点和难点。However, current epoxy coatings are not able to meet the higher requirements for corrosion resistance and wear resistance. Therefore, the development of a high-performance epoxy ceramic anti-corrosion coating with high temperature resistance and excellent anti-corrosion and wear resistance is the key point and difficulty in the research of anti-corrosion coating for ductile iron pipe for conveying corrosive water in high temperature environment.
发明内容Summary of the invention
本发明要解决的技术问题是提供具有防腐内涂层的球墨铸铁管及其生产工艺,通过在球墨铸铁管内壁涂覆本发明的环氧陶瓷涂料层,使其具有优异的抗高温性、防腐性、耐磨性,表面光滑,可减小水与管壁的摩擦阻力,从而保证管线长久的使用寿命。The technical problem to be solved by the invention is to provide a ductile iron pipe with an anti-corrosion inner coating and a production process thereof, and the epoxy resin coating layer of the invention is coated on the inner wall of the ductile iron pipe to have excellent high temperature resistance and corrosion resistance. Sexual, wear-resistant, smooth surface, can reduce the frictional resistance between water and pipe wall, thus ensuring the long service life of the pipeline.
本发明所采取的技术方案是:具有防腐涂层的球墨铸铁管,包括球墨铸铁管本体,其两端为承口和插口,球墨铸铁管内壁涂覆有本发明的环氧陶瓷涂料层。The technical solution adopted by the invention is: a ductile iron pipe with an anti-corrosion coating, comprising a ductile iron pipe body, the two ends of which are a socket and a socket, and the inner wall of the ductile iron pipe is coated with the epoxy ceramic coating layer of the invention.
通常使用的酚醛环氧涂料层有溶剂型和无溶剂型两种。由于酚醛型环氧树脂的环氧基团基本≥2,粘度相对较大,因此通常将其制作为溶剂型涂料,而溶剂型的酚醛环氧涂料有一般溶剂型涂料的共有缺点,就是不能厚涂,一次涂覆膜厚大约≤200μm,并且在溶剂挥发的过程中,在涂层中会留下较多的通道,这两个缺点都会严重影响涂层的防腐性能,对于要求使用几十年甚至百年的球墨铸铁管,不能达到需求的长久防腐效果。如果要达到重防腐效果的厚涂,必须采用多遍涂覆,无法实现球墨铸铁管批量流水线生产。The commonly used phenolic epoxy coating layers are both solvent-based and solvent-free. Since the epoxy group of the novolac type epoxy resin is substantially ≥ 2 and has a relatively high viscosity, it is usually prepared as a solvent-based paint, and the solvent-based phenolic epoxy paint has a common disadvantage of a general solvent-based paint, that is, it cannot be thick. Coating, the thickness of a single coating is about ≤200μm, and in the process of solvent evaporation, there will be more channels in the coating. These two disadvantages will seriously affect the corrosion resistance of the coating. Even a century of ductile iron pipes can not achieve the long-term anti-corrosion effect of demand. If a thick coating of heavy anti-corrosion effect is to be achieved, multi-pass coating must be used, and batch production of ductile iron pipes cannot be realized.
目前也有被称为“无溶剂型”的酚醛环氧涂层。因为一般多官能度的酚醛环氧树脂,其粘度较大,通常这样的涂料中均会加入较大量的苯甲醇(非反应型稀释剂,由于其沸点较高,会滞留在涂层中)。但这些被称为无溶剂型的酚醛环氧涂层不是真正意义的无溶剂。一些标准规定将能达到质量固含量≥95%的涂层定义为无溶剂涂层,即加入少量的苯甲醇或溶剂。通过实验发现即使加入少量苯甲醇,也就是相关标准规定的无溶剂环氧涂料(质量固含量≥95%),也会降低固化物的力学性能、耐溶剂和耐化学性能,尤其是耐高温性能。There is also a phenolic epoxy coating known as "solvent free". Because of the high viscosity of the general polyfunctional phenolic epoxy resin, a relatively large amount of benzyl alcohol (a non-reactive diluent, which is retained in the coating due to its high boiling point) is usually added to such a coating. But these so-called solvent-free phenolic epoxy coatings are not really solvent-free. Some standards stipulate that a coating that achieves a mass solids content of ≥95% is defined as a solvent-free coating, ie a small amount of benzyl alcohol or a solvent is added. It has been found through experiments that even if a small amount of benzyl alcohol is added, the solvent-free epoxy coating (quality solid content ≥95%) specified in the relevant standards will reduce the mechanical properties, solvent resistance and chemical resistance of the cured product, especially the high temperature resistance. .
本发明的无溶剂酚醛环氧陶瓷涂层达到真正的没有溶剂添加,从而达到质量固含量≥98%,甚至达到≥99%的水平。The solvent-free phenolic epoxy ceramic coating of the present invention achieves true solvent-free addition, thereby achieving a mass solid content of ≥98%, even reaching a level of ≥99%.
本发明的无溶剂酚醛环氧陶瓷涂料为环氧树脂组分(A组分)与胺固化剂组分(B组分)的双组份环氧涂料时,其中环氧树脂组分中含有酚醛环氧树脂,所用酚醛环氧树脂的环氧当量为160-190,并且酚醛环氧树脂在环氧树脂组分中的含量(重量份)在20%-60%。实验发现,本发明的无溶剂酚醛环氧陶瓷涂层能显著提高涂层的交联密度,提高了涂层的Tg,使涂层具有耐高温性能,且具有优异的耐腐蚀性,比以前的涂料层提高管道的耐腐蚀性和耐高温性。The solventless phenolic epoxy ceramic coating of the present invention is a two component epoxy coating of an epoxy resin component (component A) and an amine curing agent component (component B), wherein the epoxy resin component contains phenolic acid. The epoxy resin, the epoxy equivalent of the novolac epoxy resin used is 160-190, and the content (parts by weight) of the novolac epoxy resin in the epoxy resin component is 20% to 60%. It has been found that the solvent-free phenolic epoxy ceramic coating of the invention can significantly improve the crosslinking density of the coating, improve the Tg of the coating, make the coating have high temperature resistance, and have excellent corrosion resistance, compared with the previous The coating layer improves the corrosion resistance and high temperature resistance of the pipe.
通常为了提高管道涂层的耐磨性,会在涂层中添加一些陶瓷粉。目前通常的陶瓷粉为二氧化钛、滑石粉(主要成分为硅酸镁)、碳酸钙和二氧化硅中的一种或几种,这些是涂料所用的公知填料,其中二氧化钛一般作为颜料所用;滑石粉的作用主要是减少涂料的应力收缩;而碳酸钙作为填料具有较好的遮盖力,能很好的降低涂料的成本;二氧化硅可以降低涂层的内应力,防止开裂。现有技术采用陶瓷粉对材料的纯度没有要求,并且使用量在0.2-30%总涂料重量的含量范围,使用量小。Usually in order to improve the wear resistance of the pipe coating, some ceramic powder is added to the coating. The current common ceramic powder is one or more of titanium dioxide, talc (mainly composed of magnesium silicate), calcium carbonate and silica. These are known fillers used in coatings, of which titanium dioxide is generally used as a pigment; talcum powder The main role is to reduce the stress shrinkage of the coating; while calcium carbonate as a filler has better hiding power, which can reduce the cost of the coating; silica can reduce the internal stress of the coating and prevent cracking. The prior art uses ceramic powder to have no requirement for the purity of the material, and the amount used is in the range of 0.2-30% of the total coating weight, and the amount used is small.
本发明通过实验比较发现,虽然不添加陶瓷粉的酚醛环氧涂层已经大大提高了涂层的本身性能,但发现当使用的陶瓷粉为石英粉或/和α-Al 2O 3时,特别是所述α-Al 2O 3纯度质量百分比≥98%,所述石英粉SiO 2纯度质量百分比≥99%时,尤其是高纯度的三氧化二铝(即刚玉), 涂层产生了极高的耐磨性。这些陶瓷粉末在涂料行业并不经常使用,尽管一些涂料行业使用含有三氧化二铝,但是都是使用纯度不高的铝矾土,其三氧化二铝含量很低,不具备刚玉一样的耐磨性。并且所用陶瓷粉体积为涂层体积的20%-40%之间(占涂层重量的40%-55%之间),涂层具有优异的耐磨性,也可显著减少无溶剂涂料固化过程的应力收缩。这是由于当陶瓷粉用量较小时(<20%涂层体积,即陶瓷粉重量约<40%涂料重量),涂层的耐磨性不能得到保证;当陶瓷粉用量大时,超过涂层体积的40%,基料不能很好的包裹颜填料,涂层透气性增加,并且涂料粘度急剧上升。因此虽然本发明的无溶剂酚醛环氧涂层即使采用本发明的涂装工艺设备,也不能达到很好的效果。 The present invention finds through experiments that although the phenolic epoxy coating without adding ceramic powder has greatly improved the performance of the coating itself, it was found that when the ceramic powder used is quartz powder or / and α-Al 2 O 3 , Is the α-Al 2 O 3 purity mass percentage ≥98%, the quartz powder SiO 2 purity mass percentage ≥99%, especially the high-purity aluminum oxide (ie corundum), the coating is extremely high Wear resistance. These ceramic powders are not often used in the coatings industry, although some coatings use aluminum oxide, but they are all made of low-purity bauxite, which has a low content of aluminum oxide and is not wear-resistant like corundum. Sex. And the volume of ceramic powder used is between 20% and 40% of the coating volume (between 40% and 55% of the coating weight). The coating has excellent wear resistance and can also significantly reduce the curing process of solvent-free coatings. Stress contraction. This is because when the amount of ceramic powder is small (<20% coating volume, that is, the weight of ceramic powder is about <40% coating weight), the wear resistance of the coating cannot be guaranteed; when the amount of ceramic powder is large, the coating volume is exceeded. 40% of the base material does not wrap the pigment and filler well, the permeability of the coating increases, and the viscosity of the coating rises sharply. Therefore, although the solventless phenolic epoxy coating of the present invention does not achieve good results even with the coating process equipment of the present invention.
因此通过实验比较发现,本发明使用的陶瓷粉与通常使用的管道涂层陶瓷粉不同的是:能够改善滑石粉的易粉化;避免碳酸钙易与其它物质反应(例如酸性物质),不耐强腐蚀介质的侵蚀,在涂料中会影响涂料的耐酸性和耐水性等。本发明的涂层可以增加使用量达到更好的耐磨性、减小涂层的内应力。Therefore, through experimental comparison, it is found that the ceramic powder used in the present invention is different from the commonly used pipe coating ceramic powder in that it can improve the pulverization of talc powder; avoid the reaction of calcium carbonate with other substances (such as acidic substances), and is intolerant. The erosion of strong corrosive media can affect the acid resistance and water resistance of the coating in the coating. The coating of the present invention can increase the amount of use to achieve better wear resistance and reduce the internal stress of the coating.
进一步发现当将本发明的涂层控制到一定厚度时,非常有益。通常,钢制管道涂层的厚度为400μm左右,为了满足埋地钢制管道长久防腐效果,除了采用通常厚度的涂层外,还必须辅助采用阴极保护,才能达到需要的防腐年限,但仍希望防腐涂层能延长防腐时间。同时阴极保护的使用,增加了管线的运营成本。It has further been found to be very beneficial when controlling the coating of the present invention to a certain thickness. Generally, the thickness of the steel pipe coating is about 400 μm. In order to meet the long-term anti-corrosion effect of the buried steel pipe, in addition to the coating of the usual thickness, it is necessary to assist the cathodic protection to achieve the required corrosion protection period, but still hope Anti-corrosion coatings extend the corrosion protection time. At the same time, the use of cathodic protection increases the operating cost of the pipeline.
对于常用的溶剂型和无溶剂型环氧涂料层,如果过厚会导致涂层的内应力大,易造成涂层的开裂剥离等问题。但本发明提供的涂层由于所用陶瓷粉体积为涂层体积的20%—40%之间(占涂层重量的40%-55%之间),涂层具有优异的耐磨性,同时可显著减少无溶剂涂料固化过程的应力收缩,以达到涂层厚度为≥500μm,优选为500μm~2000μm,更优选为1000μm~1500μm。涂层厚度与涂层的防腐性能具有密切的相关性,涂层越厚,防腐性能越好,尤其对于球墨铸铁管来说,其离心铸造的固有缺点是内壁的渣坑、凸起、翘皮等,当内磨抛丸后,局部地区表面粗糙度相比钢管高很多,如果采用钢制管道的涂层厚度,在波峰位置,涂层的厚度相对很薄,这些会造成涂层的防腐性能下降;同时由于球墨铸铁管为承插式接口,不是一个大的导电体,阴极保护存在很大难度,因此提高涂层的厚度,也是保证管线使用寿命达到100年的方案之一。根据所述的具有防腐涂层的球墨铸铁管,所述高性能环氧陶瓷涂料层所用涂料为无溶剂酚醛环氧陶瓷涂料。For the commonly used solvent-based and solvent-free epoxy coating layers, if the thickness is too thick, the internal stress of the coating will be large, which may cause problems such as cracking and peeling of the coating. However, the coating provided by the present invention has excellent wear resistance due to the volume of the ceramic powder used being between 20% and 40% of the coating volume (between 40% and 55% of the coating weight). The stress shrinkage of the solventless coating curing process is remarkably reduced to achieve a coating thickness of ≥ 500 μm, preferably 500 μm to 2000 μm, more preferably 1000 μm to 1500 μm. The thickness of the coating has a close correlation with the anti-corrosion performance of the coating. The thicker the coating, the better the corrosion resistance. Especially for ductile iron pipes, the inherent disadvantages of centrifugal casting are the slag pits, bumps and bumps on the inner wall. Etc., when the internal grinding shot blasting, the surface roughness of the local area is much higher than that of the steel pipe. If the coating thickness of the steel pipe is used, the thickness of the coating is relatively thin at the peak position, which will cause the corrosion resistance of the coating. At the same time, because the ductile iron pipe is a socket-type interface, it is not a large electrical conductor. Cathodic protection is very difficult. Therefore, increasing the thickness of the coating is also one of the solutions to ensure the service life of the pipeline reaches 100 years. According to the ductile iron pipe with anticorrosive coating, the coating used for the high performance epoxy ceramic coating layer is a solventless phenolic epoxy ceramic coating.
因此,本发明提供了一种具有防腐内涂层以及涂覆该涂层的球墨铸铁管,所述球墨铸铁管内壁涂覆环氧涂料层,所用涂料为无溶剂酚醛环氧涂料,优选无溶剂酚醛环氧陶瓷涂料。Accordingly, the present invention provides a ductile iron pipe having an anticorrosive inner coating layer coated with an epoxy coating layer on the inner wall of the ductile iron pipe, and the coating used is a solventless phenolic epoxy coating, preferably solvent free Phenolic epoxy ceramic coating.
根据所述的具有防腐内涂层的球墨铸铁管,所述高性能环氧陶瓷涂料层的体积固体份含量≥98%,优选≥99%。According to the ductile iron pipe having the anticorrosive inner coating, the high-performance epoxy ceramic coating layer has a volume solid content of ≥98%, preferably ≥99%.
根据所述的具有防腐内涂层的球墨铸铁管,所述高性能环氧陶瓷涂料层所用涂料为无溶剂酚醛环氧陶瓷涂料,其中作为填料的陶瓷粉体积为涂层体积的20%-40%,优选为20%-30%。According to the ductile iron pipe with anticorrosive inner coating, the coating for the high performance epoxy ceramic coating layer is a solventless phenolic epoxy ceramic coating, wherein the ceramic powder as a filler has a volume of 20%-40 of the coating volume. %, preferably 20% to 30%.
根据所述的具有防腐内涂层的球墨铸铁管,所述高性能环氧陶瓷涂料层所用涂料为无溶剂酚醛环氧陶瓷涂料,其中作为填料的陶瓷粉为石英粉或/和α-Al 2O 3,所述α-Al 2O 3纯度质量百分比≥98%;所述石英粉SiO 2纯度质量百分比≥99%。. According to the ductile iron pipe having an anticorrosive inner coating layer, the coating for the high performance epoxy ceramic coating layer is a solventless phenolic epoxy ceramic coating, wherein the ceramic powder as a filler is quartz powder or/and α-Al 2 O 3 , the α-Al 2 O 3 purity mass percentage ≥98%; the quartz powder SiO 2 purity mass percentage ≥99%. .
根据所述的具有防腐内涂层的球墨铸铁管,所述高性能环氧陶瓷涂料层所用无溶剂酚醛环氧陶瓷涂料为双组份涂料,其中一个组分为环氧树脂组分,一个组分为胺固化剂组分,并且环氧树脂组分(A组分)与胺固化剂组分(B组分)的比例为1:1(重量比)。According to the ductile iron pipe having an anticorrosive inner coating layer, the solventless phenolic epoxy ceramic coating used in the high performance epoxy ceramic coating layer is a two component coating, wherein one component is an epoxy resin component, one group Divided into an amine curing agent component, and the ratio of the epoxy resin component (A component) to the amine curing agent component (B component) is 1:1 (weight ratio).
根据所述的具有防腐内涂层的球墨铸铁管,所述高性能环氧陶瓷涂料层所用无溶剂酚醛环氧陶瓷涂料为双组份环氧涂料,其中环氧树脂组分中含有酚醛环氧树脂,所用酚醛环氧树脂的环氧当量为160-190,并且酚醛环氧树脂在环氧树脂组分中的含量(重量份)在20%-60%。According to the ductile iron pipe with anticorrosive inner coating, the solventless phenolic epoxy ceramic coating used in the high performance epoxy ceramic coating layer is a two component epoxy coating, wherein the epoxy resin component contains phenolic epoxy The resin, the epoxy equivalent of the novolac epoxy resin used is 160-190, and the content (parts by weight) of the novolac epoxy resin in the epoxy resin component is 20% to 60%.
根据所述的具有防腐涂层的球墨铸铁管,所述高性能酚醛环氧陶瓷涂料的环氧树脂组分(A组分),包括:According to the ductile iron pipe having an anticorrosive coating, the epoxy resin component (component A) of the high performance phenolic epoxy ceramic coating comprises:
酚醛环氧树脂:20-60%;Phenolic epoxy resin: 20-60%;
液体双酚A环氧树脂:0-25%;Liquid bisphenol A epoxy resin: 0-25%;
活性稀释剂:7-12%;Reactive diluent: 7-12%;
助剂:2-3%;Auxiliary: 2-3%;
颜料:11-14%;Pigment: 11-14%;
陶瓷粉:20-34%。Ceramic powder: 20-34%.
其中,所述助剂为润湿分散剂、防沉剂、消泡剂中的一种或几种的混合物。Wherein, the auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent.
其中的酚醛环氧树脂的环氧当量为160-190的酚醛环氧树脂。这种酚醛环氧树脂,官能度高,增加了涂层的交联密度,提高了涂层的Tg,使涂层具有耐高温性能,和优异的耐腐蚀性,尤其是耐酸性。The phenolic epoxy resin has a phenolic epoxy resin having an epoxy equivalent of 160-190. The phenolic epoxy resin has high functionality, increases the crosslink density of the coating, improves the Tg of the coating, imparts high temperature resistance to the coating, and excellent corrosion resistance, especially acid resistance.
其中的双酚A环氧树脂的环氧当量为190液体环氧树脂,例如DER 331。The epoxy equivalent of the bisphenol A epoxy resin is 190 liquid epoxy resin, such as DER 331.
其中的活性稀释剂为环氧当量为175-330的缩水甘油醚反应型活性稀释剂,该类活性稀释剂对无溶剂环氧树脂的稀释能力强,能够有效降低体系的粘度,并且可以增加体系的柔韧性,提高涂层的抗冲击能力,同时避免了由于使用非活性稀释剂带来的毒性。常用的市售产品有:聚丙二醇二缩水甘油醚,例如DOW的DER 732,邻甲苯基缩水甘油醚,例如HELOXY62。The reactive diluent is a glycidyl ether reactive reactive diluent having an epoxy equivalent of 175-330. The reactive diluent has strong dilution ability to the solventless epoxy resin, can effectively reduce the viscosity of the system, and can increase the system. The flexibility increases the impact resistance of the coating while avoiding the toxicity due to the use of inert diluents. Commonly used commercial products are: polypropylene glycol diglycidyl ether, such as DER 732 of DOW, o-tolyl glycidyl ether, such as HELOXY 62.
本发明根据具体用途加入适当的颜料。选择对人体无害的金红石钛白粉R-930、炭黑,根据涂膜的颜色要求,它们可是一种单用或者两种并用。The present invention incorporates suitable pigments depending on the particular application. The rutile titanium dioxide R-930 and carbon black which are harmless to the human body are selected, and they may be used alone or in combination according to the color requirements of the coating film.
所述的陶瓷粉为石英粉或/和α-Al 2O 3The ceramic powder is quartz powder or/and α-Al 2 O 3 .
根据所述的具有防腐涂层的球墨铸铁管,所述胺固化剂组分(B组分),包括:According to the ductile iron pipe having an anticorrosive coating, the amine curing agent component (component B) comprises:
胺固化剂:22-30%;Amine curing agent: 22-30%;
催化剂:0-2%Catalyst: 0-2%
陶瓷粉:65-75%;Ceramic powder: 65-75%;
助剂:3-4%;Additives: 3-4%;
所述的胺固化剂为特殊制备的改性胺固化剂,可为曼尼期碱或/和改性脂环胺,曼尼期碱具有低温固化性,以及对潮湿面具有优异的附着力、与树脂具有兼容性好的特点;脂环胺可提高涂层的Tg,从而提高涂层的耐热性能和高温附着力。The amine curing agent is a specially prepared modified amine curing agent, which can be Mannich base or/and modified alicyclic amine, Mannich base has low temperature curability, and has excellent adhesion to wet surfaces, It has good compatibility with the resin; alicyclic amine can increase the Tg of the coating, thereby improving the heat resistance and high temperature adhesion of the coating.
所述催化剂为叔胺催化剂,例如Ancamine K54。The catalyst is a tertiary amine catalyst such as Ancamine K54.
助剂为润湿分散剂、防沉剂、消泡剂中的一种或几种的混合物。The auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent.
所述的陶瓷粉为石英粉或/和α-Al 2O 3The ceramic powder is quartz powder or/and α-Al 2 O 3 .
所述的无溶剂酚醛环氧陶瓷涂料配制成A/B两组分,在使用时按照重量比A:B=1:1的配比混合。The solvent-free phenolic epoxy ceramic coating is formulated into two components of A/B, and is mixed at a weight ratio of A:B=1:1 in use.
根据所述的具有防腐内涂层的球墨铸铁管的生产工艺,所述高性能环氧涂料层的涂覆程序如下:According to the production process of the ductile iron pipe with the anticorrosive inner coating, the coating procedure of the high performance epoxy coating layer is as follows:
(1)球墨铸铁管内磨;(1) Grinding of ductile iron pipe;
(2)球墨铸铁管内壁进行喷砂或抛丸;(2) Sandblasting or shot blasting on the inner wall of ductile iron pipe;
(3)预热,使球墨铸铁管管温在30℃-70℃;(3) preheating, so that the temperature of the ductile iron pipe is between 30 ° C and 70 ° C;
(4)内壁渣坑等缺陷的修补;(4) Repair of defects such as slag pits in the inner wall;
(5)管子以一定速度进行旋转,转速为线速度≥250m/min;(5) The pipe is rotated at a certain speed, and the rotational speed is a linear velocity ≥ 250 m/min;
(6)A、B组分均需预热至45-55℃;(6) A and B components need to be preheated to 45-55 ° C;
(7)采用双组份喷涂设备,将环氧树脂组分和固化剂组分分别输送至喷头,通过电机或空气马达带动喷杯高速旋转使涂料混合雾化,喷涂至管子上;(7) using a two-component spraying device, respectively conveying the epoxy resin component and the curing agent component to the nozzle, and driving the spray cup to rotate at a high speed by a motor or an air motor to atomize and spray the coating onto the pipe;
(8)喷涂后管子继续旋转10-40min,使涂料充分流平;(8) After spraying, the tube continues to rotate for 10-40 minutes to fully level the paint;
(9)固化:涂覆后的球墨铸铁管需在烘房中提高温度加速固化,固化条件为:固化温度为50-90℃,固化1h以上;优选的固化条件为:温度为75-85℃,固化2h;然后室温固化7d,即可投入使用。(9) Curing: The coated ductile iron pipe needs to be heated and accelerated in the drying room. The curing conditions are: curing temperature is 50-90 ° C, curing for more than 1 h; preferred curing conditions are: temperature is 75-85 ° C , curing for 2h; then curing at room temperature for 7d, ready to use.
同现有技术相比,本发明的突出效果在于:Compared with the prior art, the outstanding effects of the present invention are:
1)本发明提供的防腐涂层,是在球铁管内壁喷涂高性能酚醛环氧陶瓷涂料层,此涂料对球墨铸铁管具有优异的附着力,采用ASTM D4541进行拉拔强度的测试,其常温拉拔附着力可达15Mpa以上,高温拉拔附着力(80℃)可达4Mpa以上。1) The anti-corrosion coating provided by the invention is a high-performance phenolic epoxy ceramic coating layer sprayed on the inner wall of the ductile iron pipe. The coating has excellent adhesion to the ductile iron pipe, and the tensile strength is tested by ASTM D4541, and the room temperature is tested. Pulling adhesion can reach more than 15Mpa, and high-temperature drawing adhesion (80°C) can reach more than 4Mpa.
2)本发明提供的高性能酚醛环氧陶瓷涂料,由于不含溶剂,可使一次成膜厚度达到2000μm。2) The high-performance phenolic epoxy ceramic coating provided by the present invention can achieve a film thickness of 2000 μm at one time because it does not contain a solvent.
3)此涂层由于石英粉或/和α-Al 2O 3陶瓷粉填料的加入,并且其体积含量占涂层总体积高达20%以上,赋予了涂层优异的耐磨性,根据ASTM D4060检测,采用CS-17轮,载荷1kg,1000转,磨损量≤50mg。 3) This coating is given by the addition of quartz powder or / and α-Al 2 O 3 ceramic powder filler, and its volume content accounts for more than 20% of the total volume of the coating, giving the coating excellent wear resistance according to ASTM D4060 Test, using CS-17 wheel, load 1kg, 1000 rpm, wear amount ≤ 50mg.
4)同样由于本发明提供的高性能酚醛环氧陶瓷内防腐涂层球墨铸铁管,内壁光滑,能有效降低水介质与管壁之间的摩擦阻力,节约输送能源。4) Also, the high performance phenolic epoxy ceramic inner anticorrosive coated ductile iron pipe provided by the invention has smooth inner wall, can effectively reduce the frictional resistance between the water medium and the pipe wall, and saves transportation energy.
5)本发明提供的高性能酚醛环氧陶瓷内防腐涂层,以酚醛环氧为基础成膜物质,环氧基含量高,增加了涂层的交联密度,提高了涂层的Tg,使涂层具有耐高温性能,本发明提供的涂层,可用于长期输送80℃的水介质。5) The high performance phenolic epoxy ceramic inner anticorrosive coating provided by the invention is based on a phenolic epoxy film-forming material, has a high epoxy content, increases the crosslink density of the coating, and improves the Tg of the coating. The coating has high temperature resistance, and the coating provided by the present invention can be used for long-term transportation of an aqueous medium of 80 °C.
6)同样本发明提供的高性能酚醛环氧陶瓷内防腐涂层,以酚醛环氧为基础成膜物质,增加了涂层的交联密度,并且由于陶瓷粉的加入,可赋予该涂层优异的防腐蚀性,从而保证球墨铸铁管的100年寿命。6) The high-performance phenolic epoxy ceramic inner anticorrosive coating provided by the invention also has a phenolic epoxy-based film-forming substance, which increases the cross-linking density of the coating, and is excellent in the coating due to the addition of the ceramic powder. The corrosion resistance ensures the 100-year life of ductile iron pipes.
7)本发明提供的高性能酚醛环氧陶瓷涂料,不含任何有机溶剂,安全、环保、卫生,经国内外权威机构检测,满足GB 17219/T生活饮用水输配水设备及防护材料安全性评价标准要求,可用于饮用水的输送。7) The high performance phenolic epoxy ceramic coating provided by the invention does not contain any organic solvent, is safe, environmentally friendly and hygienic, and is tested by domestic and foreign authorities to meet the safety of GB 17219/T drinking water distribution equipment and protective materials. The evaluation criteria require that it be used for the delivery of drinking water.
下面结合具体实施例对本发明的具有防腐内涂层的球墨铸铁管及其生产工艺作进一步说明。The ductile iron pipe with anticorrosive inner coating of the present invention and the production process thereof will be further described below in conjunction with specific embodiments.
具体实施方式detailed description
应用于输水管道的环氧陶瓷涂料防腐内涂层的球墨铸铁管用如下方法制备。制备方法包括如下步骤:The ductile iron pipe of the epoxy ceramic coating anticorrosive inner coating applied to the water pipeline is prepared as follows. The preparation method comprises the following steps:
(1)球墨铸铁管内磨;(1) Grinding of ductile iron pipe;
(2)球墨铸铁管内壁进行喷砂或抛丸,使粗糙度Rz≥60μm;(2) sandblasting or shot blasting on the inner wall of the ductile iron pipe, so that the roughness Rz≥60μm;
(3)预热,使球墨铸铁管管温在30℃-70℃;(3) preheating, so that the temperature of the ductile iron pipe is between 30 ° C and 70 ° C;
(4)内壁渣坑等缺陷的修补,采用所用高性能环氧陶瓷涂料,加入适量陶瓷粉,调整到适当的粘度对表面缺陷进行修补;(4) Repair of defects such as slag pits in the inner wall, use high-performance epoxy ceramic coatings, add appropriate amount of ceramic powder, and adjust to appropriate viscosity to repair surface defects;
(5)管子以一定速度进行旋转,转速为线速度≥250m/min;(5) The pipe is rotated at a certain speed, and the rotational speed is a linear velocity ≥ 250 m/min;
(6)高性能酚醛环氧陶瓷涂料在常温下粘度较大,必须进行预热:A、B组分均需预热至45-55℃,以降低粘度;(6) High-performance phenolic epoxy ceramic coatings have high viscosity at room temperature and must be preheated: components A and B must be preheated to 45-55 ° C to reduce viscosity;
(7)采用双组份喷涂设备,将A组分(环氧树脂组分)和B组分(固化剂组分)分别输送至喷头,通过电机或空气马达带动喷杯高速旋转使涂料混合雾化,喷涂至旋转的管子上;(7) Using a two-component spraying equipment, the A component (epoxy resin component) and the B component (curing agent component) are separately delivered to the nozzle, and the spray cup is rotated at a high speed by a motor or an air motor to mix the coating mist. Sprayed onto a rotating tube;
(8)喷涂后管子继续旋转10-40min,使涂料充分流平,并且停止后不留挂,进入固化工序;(8) After spraying, the tube continues to rotate for 10-40 minutes, so that the paint is fully leveled, and does not remain hanging after stopping, and enters the curing process;
(9)固化:喷涂后的球墨铸铁管需在烘房中提高温度加速固化,固化条件为:固化温度为50-90℃,固化1h以上,然后室温固化7d;优选的固化条件为:温度为75-85℃,固化2h,然后室温固化7d,即可投入使用。(9) Curing: After spraying, the ductile iron pipe needs to be heated in the drying room to accelerate the curing. The curing conditions are: curing temperature is 50-90 ° C, curing for more than 1 h, and then curing at room temperature for 7 d; the preferred curing conditions are: temperature is Curing at 75-85 ° C for 2 h, then curing at room temperature for 7 d, ready for use.
其中高性能酚醛环氧陶瓷涂料的制造过程如下:The manufacturing process of the high performance phenolic epoxy ceramic coating is as follows:
A组分:环氧树脂组分,包括酚醛环氧树脂、或酚醛环氧树脂与液体双酚A环氧树脂的混合物、活性稀释剂、助剂、颜料、陶瓷粉。将酚醛环氧树脂、或酚醛环氧树脂与液体双酚A环氧树脂加入分散缸中,中速搅拌均匀;在慢速搅拌下加入相关助剂(包括润湿分散剂、消泡剂),待搅拌均匀后,加入所需的颜料、填料,高速分散至所需细度,然后加入剩余的助剂等材料中速分散均匀,过滤包装即成A组分。Component A: epoxy resin component, including novolac epoxy resin, or a mixture of phenolic epoxy resin and liquid bisphenol A epoxy resin, reactive diluent, auxiliary agent, pigment, ceramic powder. Add phenolic epoxy resin, or phenolic epoxy resin and liquid bisphenol A epoxy resin to the dispersion tank, and stir evenly at medium speed; add relevant additives (including wetting and dispersing agent, defoaming agent) under slow stirring. After the mixture is evenly stirred, the desired pigment and filler are added, and the desired fineness is dispersed at a high speed, and then the remaining auxiliary materials and the like are uniformly dispersed in a medium speed, and the filter package is formed into the A component.
B组分:胺固化剂组分,包括曼尼期碱胺固化剂、陶瓷粉、助剂;或包括改性脂环胺固化剂、陶瓷粉、助剂。Component B: an amine curing agent component, including a Mannich base amine curing agent, a ceramic powder, an auxiliary agent; or a modified alicyclic amine curing agent, a ceramic powder, and an auxiliary agent.
将曼尼期碱/或改性脂环胺固化剂放入分散缸中,中速搅拌均匀;在慢速搅拌下加入分散剂、消泡剂等助剂,待搅拌均匀后,加入所需的陶瓷粉,高速分散至所需细度,然后加入剩余的助剂等材料中速分散均匀,过滤包装。Put the Mannich base/modified alicyclic amine curing agent into the dispersing tank and stir evenly at medium speed; add the dispersant, defoaming agent and other additives under slow stirring, and after adding evenly, add the required The ceramic powder is dispersed at a high speed to the desired fineness, and then the remaining auxiliary materials and the like are uniformly dispersed in a medium speed, and the package is filtered.
采用上述方法进行优选高性能酚醛环氧陶瓷涂料实施例的生产,并按照上述方式进行涂覆获得本发明的防腐涂层球墨铸铁管及其性能。The production of the preferred high performance phenolic epoxy ceramic coating examples was carried out by the above method, and coated in the above manner to obtain the anticorrosive coated ductile iron pipe of the present invention and its properties.
实施例1Example 1
按照制备实施例的方法制备以下所给出的涂层材料并进行涂覆,涂覆后进行效果比较。与本发明所给出涂层材料不同的涂层材料,根据本领域的常规技术,按照与本发明类似的方法制备。The coating materials given below were prepared and coated according to the method of the Preparation Examples, and the effects were compared after coating. A coating material different from the coating material given by the present invention is prepared according to a method similar to the present invention according to a conventional technique in the art.
表1Table 1
Figure PCTCN2018086787-appb-000001
Figure PCTCN2018086787-appb-000001
Figure PCTCN2018086787-appb-000002
Figure PCTCN2018086787-appb-000002
Figure PCTCN2018086787-appb-000003
Figure PCTCN2018086787-appb-000003
对比例1是一种“溶剂型涂层”,对比例2是目前常规使用的无溶剂涂层。可以看出溶剂型涂层在涂装工艺上、耐酸、耐蒸馏水性方面以及耐磨性、耐高温性方面都比不含溶剂的涂层材料差。对比例2所代表的目前通常使用的“不含溶剂型涂层”虽然改善了溶剂型涂层的一些性能,但其一方面仍含有不希望存在的非活性稀释剂,但在耐酸性、耐水性方面以及耐磨性、耐高温性方面仍不令人满意。本发明的无溶剂涂层能克服现有涂层的不满意之处,在耐磨性、耐腐蚀性,尤其是耐高温性附着力方面有了极大提高。Comparative Example 1 is a "solvent-type coating", and Comparative Example 2 is a solventless coating currently conventionally used. It can be seen that the solvent-based coating is inferior to the solvent-free coating material in terms of coating process, acid resistance, distillation resistance, and abrasion resistance and high temperature resistance. The "solvent-free coating" currently used in Comparative Example 2, although improving some properties of the solvent-based coating, still contains an undesired inactive diluent on the one hand, but is resistant to acid and water. Sexual aspects as well as wear resistance and high temperature resistance are still unsatisfactory. The solventless coating of the present invention overcomes the dissatisfaction of the prior coatings and greatly improves the wear resistance, corrosion resistance, and particularly high temperature adhesion.
实施例2Example 2
表2Table 2
Figure PCTCN2018086787-appb-000004
Figure PCTCN2018086787-appb-000004
Figure PCTCN2018086787-appb-000005
Figure PCTCN2018086787-appb-000005
Figure PCTCN2018086787-appb-000006
Figure PCTCN2018086787-appb-000006
对比例3、4使用的是目前现有技术常规使用陶瓷粉的涂层。但可以看出常规使用的陶瓷粉在制备时工艺存在较大的不便操作性,并且现有陶瓷粉碳酸钙易与其它物质反应(例如酸性物质),不耐强腐蚀介质的侵蚀,在涂料中会影响涂料的耐酸性和耐水性;滑石粉、碳酸钙相对本发明要求的高纯度的陶瓷粉材料硬度低,因此在机械性能和耐化侵性方面明显弱于本发明采用的涂层。Comparative Examples 3 and 4 used a coating which is conventionally used in the prior art for ceramic powder. However, it can be seen that the conventionally used ceramic powder has a large inconvenience in the process of preparation, and the existing ceramic powder calcium carbonate is easily reacted with other substances (for example, an acidic substance), and is not resistant to the corrosion of a highly corrosive medium in the coating. It will affect the acid resistance and water resistance of the coating; the talc powder and calcium carbonate have lower hardness than the high-purity ceramic powder material required by the present invention, and thus are significantly weaker in mechanical properties and chemical resistance than the coating used in the present invention.
实施例3Example 3
表3table 3
Figure PCTCN2018086787-appb-000007
Figure PCTCN2018086787-appb-000007
Figure PCTCN2018086787-appb-000008
Figure PCTCN2018086787-appb-000008
Figure PCTCN2018086787-appb-000009
Figure PCTCN2018086787-appb-000009
小结:通过实验可以看出本发明的涂层材料能够满足目前的使用需要,具有优异的耐腐蚀性、耐磨性能以及耐高温性。Summary: It can be seen through experiments that the coating material of the present invention can meet the current needs of use, and has excellent corrosion resistance, wear resistance and high temperature resistance.
以上所述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。The embodiments described above are only intended to describe the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various embodiments of the present invention may be made by those skilled in the art without departing from the spirit of the invention. Modifications and improvements are intended to fall within the scope of the invention as defined by the appended claims.
工业实用性Industrial applicability
本发明具有防腐内涂层的球墨铸铁管及其生产工艺在输水输气领域具有重大影响。本发明提供的防腐涂层,是在球铁管内壁喷涂高性能酚醛环氧陶瓷涂料层,此涂料对球墨铸铁管具有优异的附着力,采用ASTM D4541进行拉拔强度的测试,其常温拉拔附着力可达15Mpa以上,高温拉拔附着力(80℃)可达4Mpa以上。本发明具有防腐内涂层的球墨铸铁管及其生产工艺具有很强的工业实用性和可操作性,对管线运输意义重大。The ductile iron pipe with anticorrosive inner coating of the invention and the production process thereof have great influence in the field of water transportation and gas transmission. The anti-corrosion coating provided by the invention is a high-performance phenolic epoxy ceramic coating layer sprayed on the inner wall of the ductile iron pipe, the coating has excellent adhesion to the ductile iron pipe, and the tensile strength test is tested by ASTM D4541, and the normal temperature drawing is performed. The adhesion can reach more than 15Mpa, and the high-temperature drawing adhesion (80°C) can reach more than 4Mpa. The ductile iron pipe with anti-corrosion inner coating of the invention and the production process thereof have strong industrial applicability and operability, and are of great significance for pipeline transportation.

Claims (23)

  1. 一种具有防腐内涂层的球墨铸铁管,其特征在于:所述球墨铸铁管内壁涂覆环氧涂料层,所述环氧涂料层所用涂料为无溶剂酚醛环氧涂料,优选为无溶剂酚醛环氧陶瓷涂料。A ductile iron pipe with an anticorrosive inner coating, characterized in that: the inner wall of the ductile iron pipe is coated with an epoxy coating layer, and the coating for the epoxy coating layer is a solventless phenolic epoxy coating, preferably a solventless phenolic Epoxy ceramic coating.
  2. 根据权利要求1所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述无溶剂酚醛环氧陶瓷涂料的体积固体份含量≥98%,优选≥99%。The ductile iron pipe with an anti-corrosion inner coating according to claim 1, wherein the solvent-free phenolic epoxy ceramic coating has a volume solid content of ≥98%, preferably ≥99%.
  3. 根据权利要求1或2所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述无溶剂酚醛环氧陶瓷涂料为环氧树脂组分A与胺固化剂组分B的双组份环氧涂料,其中环氧树脂组分中含有酚醛环氧树脂,所用酚醛环氧树脂的环氧当量为160-190,且酚醛环氧树脂在环氧树脂组分中的重量份含量为20%-60%。The ductile iron pipe with anticorrosive inner coating according to claim 1 or 2, wherein the solventless phenolic epoxy ceramic coating is a two component of epoxy resin component A and amine curing agent component B. Epoxy coating, wherein the epoxy resin component contains a phenolic epoxy resin, the epoxy equivalent of the phenolic epoxy resin is 160-190, and the content of the phenolic epoxy resin in the epoxy resin component is 20% -60%.
  4. 根据权利要求1-3任意一项所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述无溶剂酚醛环氧陶瓷涂料中作为填料的陶瓷粉体积为涂层体积的20%-40%,优选为20%-30%。The ductile iron pipe with an anticorrosive inner coating according to any one of claims 1 to 3, wherein the volume of the ceramic powder as a filler in the solventless phenolic epoxy ceramic coating is 20% of the coating volume - 40%, preferably 20%-30%.
  5. 根据权利要求1-4任意一项所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述无溶剂酚醛环氧陶瓷涂料中作为填料的陶瓷粉为石英粉或/和α-Al 2O 3,所述α-Al 2O 3纯度质量百分比≥98%;所述石英粉SiO 2纯度质量百分比≥99%。 The ductile iron pipe with an anticorrosive inner coating according to any one of claims 1 to 4, wherein the ceramic powder as a filler in the solventless phenolic epoxy ceramic coating is quartz powder or/and α-Al. 2 O 3 , the α-Al 2 O 3 purity mass percentage ≥98%; the quartz powder SiO 2 purity mass percentage ≥99%.
  6. 根据权利要求3所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述环氧树脂组分A与胺固化剂组分B的重量比为1:1。The ductile iron pipe with an anticorrosive inner coating according to claim 3, wherein the weight ratio of the epoxy resin component A to the amine curing agent component B is 1:1.
  7. 根据权利要求5所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述的无溶剂酚醛环氧陶瓷涂料的环氧树脂组分A,包括:The ductile iron pipe with anti-corrosion inner coating according to claim 5, wherein the epoxy resin component A of the solvent-free phenolic epoxy ceramic coating comprises:
    酚醛环氧树脂:20-60%;Phenolic epoxy resin: 20-60%;
    液体双酚A环氧树脂:0-25%;Liquid bisphenol A epoxy resin: 0-25%;
    活性稀释剂:7-12%;Reactive diluent: 7-12%;
    助剂:2-3%;Auxiliary: 2-3%;
    颜料:11-14%;Pigment: 11-14%;
    陶瓷粉:20-34%。Ceramic powder: 20-34%.
  8. 根据权利要求7所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述的无溶剂酚醛环氧陶瓷涂料的环氧树脂组分A,其中,所述助剂为润湿分散剂、防沉剂、消泡剂中的一种或几种的混合物;The ductile iron pipe with anti-corrosion inner coating according to claim 7, characterized in that: the epoxy resin component A of the solvent-free phenolic epoxy ceramic coating, wherein the auxiliary agent is a wetting and dispersing agent a mixture of one or more of an anti-settling agent and an antifoaming agent;
    和/或,所述的双酚A环氧树脂的环氧当量为190液体环氧树脂;And/or, the bisphenol A epoxy resin has an epoxy equivalent of 190 liquid epoxy resin;
    和/或,所述的活性稀释剂为环氧当量为175-330的缩水甘油醚反应型活性稀释剂;And/or, the reactive diluent is a glycidyl ether reactive reactive diluent having an epoxy equivalent of 175-330;
    和/或,所述的颜料为金红石钛白粉和/或炭黑;And/or, the pigment is rutile titanium dioxide and/or carbon black;
    和/或,所述的陶瓷粉为石英粉或/和α-Al 2O 3And/or, the ceramic powder is quartz powder or/and α-Al 2 O 3 .
  9. 根据权利要求3所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述的无溶剂酚醛环氧陶瓷涂料的胺固化剂组分B,包括:The ductile iron pipe with an anti-corrosion inner coating according to claim 3, wherein the amine curing agent component B of the solvent-free phenolic epoxy ceramic coating comprises:
    胺固化剂:22-30%;Amine curing agent: 22-30%;
    催化剂:0-2%;Catalyst: 0-2%;
    陶瓷粉:65-75%;Ceramic powder: 65-75%;
    助剂:3-4%。Additives: 3-4%.
  10. 根据权利要求9所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述的无溶剂酚醛环氧陶瓷涂料的胺固化剂组分B,其中:The ductile iron pipe with an anticorrosive inner coating according to claim 9, wherein the amine curing agent component B of the solventless novolac epoxy ceramic coating comprises:
    所述催化剂为叔胺催化剂;The catalyst is a tertiary amine catalyst;
    和/或,所述助剂为润湿分散剂、防沉剂、消泡剂中的一种或几种的混合物。And/or the auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent.
    和/或,所述陶瓷粉为石英粉或/和α-Al 2O 3And/or, the ceramic powder is quartz powder or/and α-Al 2 O 3 .
  11. 根据权利要求1所述的具有防腐内涂层的球墨铸铁管,其特征在于:所述环氧涂料层厚度为≥500μm,优选为500μm~2000μm,更优选为1000μm~1500μm。The ductile iron pipe having an anticorrosive inner coating according to claim 1, wherein the epoxy coating layer has a thickness of ≥ 500 μm, preferably 500 μm to 2000 μm, more preferably 1000 μm to 1500 μm.
  12. 权利要求1-11任意一项所述的具有防腐内涂层的球墨铸铁管的生产工艺,其特征在于,包括如下步骤:The process for producing a ductile iron pipe having an anticorrosive inner coating according to any one of claims 1 to 11, characterized in that it comprises the following steps:
    (1)球墨铸铁管内磨;(1) Grinding of ductile iron pipe;
    (2)球墨铸铁管内壁进行喷砂或抛丸;(2) Sandblasting or shot blasting on the inner wall of ductile iron pipe;
    (3)预热,使球墨铸铁管管温在30℃-70℃;(3) preheating, so that the temperature of the ductile iron pipe is between 30 ° C and 70 ° C;
    (4)内壁渣坑等缺陷的修补;(4) Repair of defects such as slag pits in the inner wall;
    (5)管子以一定速度进行旋转,转速为线速度≥250m/min;(5) The pipe is rotated at a certain speed, and the rotational speed is a linear velocity ≥ 250 m/min;
    (6)A、B组分均需预热至45-55℃;(6) A and B components need to be preheated to 45-55 ° C;
    (7)采用双组份喷涂设备,将环氧树脂组分和固化剂组分分别输送至喷头,通过电机或空气马达带动喷杯高速旋转使涂料混合雾化,喷涂至管子上;(7) using a two-component spraying device, respectively conveying the epoxy resin component and the curing agent component to the nozzle, and driving the spray cup to rotate at a high speed by a motor or an air motor to atomize and spray the coating onto the pipe;
    (8)喷涂后管子继续旋转10-40min,使涂料充分流平;(8) After spraying, the tube continues to rotate for 10-40 minutes to fully level the paint;
    (9)固化:涂覆后的球墨铸铁管需在烘房中提高温度加速固化,固化条件为:固化温度为50-90℃,固化1h以上;优选的固化条件为:温度为75-85℃,固化2h;然后室温固化7d,即可投入使用。(9) Curing: The coated ductile iron pipe needs to be heated and accelerated in the drying room. The curing conditions are: curing temperature is 50-90 ° C, curing for more than 1 h; preferred curing conditions are: temperature is 75-85 ° C , curing for 2h; then curing at room temperature for 7d, ready to use.
  13. 一种环氧涂料层,其特征在于:所述环氧涂料层所用涂料为无溶剂酚醛环氧涂料,优选为无溶剂酚醛环氧陶瓷涂料。An epoxy coating layer characterized in that the coating for the epoxy coating layer is a solventless phenolic epoxy coating, preferably a solventless phenolic epoxy ceramic coating.
  14. 根据权利要求13所述的环氧涂料层,其特征在于:所述无溶剂酚醛环氧陶瓷涂料的体积固体份含量≥98%,优选≥99%。The epoxy coating layer according to claim 13, wherein the solvent-free phenolic epoxy ceramic coating has a volume solid content of ≥98%, preferably ≥99%.
  15. 根据权利要求13或14所述的环氧涂料层,其特征在于:所述无溶剂酚醛环氧陶瓷涂料为环氧树脂组分A与胺固化剂组分B的双组份环氧涂料,其中环氧树脂组分中含有酚醛环氧树脂,所用酚醛环氧树脂的环氧当量为160-190,并且酚醛环氧树脂在环氧树脂组分中的重量份含量为20%-60%。The epoxy coating layer according to claim 13 or 14, wherein the solvent-free phenolic epoxy ceramic coating is a two-component epoxy coating of epoxy resin component A and amine curing agent component B, wherein The epoxy resin component contains a novolac epoxy resin, the epoxy equivalent of the novolac epoxy resin is 160-190, and the content of the novolac epoxy resin in the epoxy resin component is 20% to 60%.
  16. 根据权利要求13-15任意一项所述的环氧涂料层,其特征在于:所述无溶剂酚醛环氧陶瓷涂料中作为填料的陶瓷粉体积为涂层体积的20%-40%,优选为20%-30%。The epoxy coating layer according to any one of claims 13-15, wherein the volume of the ceramic powder as a filler in the solventless phenolic epoxy ceramic coating is from 20% to 40% by volume of the coating, preferably 20%-30%.
  17. 根据权利要求13-16任意一项所述的环氧涂料层,其特征在于:所述无溶剂酚醛环氧陶瓷涂料中作为填料的陶瓷粉为石英粉或/和α-Al 2O 3,所述α-Al 2O 3纯度质量百分比≥98%;所述石英粉SiO 2纯度质量百分比≥99%。 The epoxy coating layer according to any one of claims 13-16, wherein the ceramic powder as a filler in the solventless phenolic epoxy ceramic coating is quartz powder or/and α-Al 2 O 3 , The α-Al 2 O 3 purity mass percentage is ≥98%; the quartz powder SiO 2 purity mass percentage is ≥99%.
  18. 根据权利要求13-16任意一项所述的环氧涂料层,其特征在于:所述环氧树脂组分A与胺固化剂组分B的重量比为1:1。The epoxy coating layer according to any one of claims 13 to 16, wherein the weight ratio of the epoxy resin component A to the amine curing agent component B is 1:1.
  19. 根据权利要求18所述的环氧涂料层,其特征在于:环氧树脂组分A,包括:The epoxy coating layer according to claim 18, wherein the epoxy resin component A comprises:
    酚醛环氧树脂:20-60%;Phenolic epoxy resin: 20-60%;
    液体双酚A环氧树脂:0-25%;Liquid bisphenol A epoxy resin: 0-25%;
    活性稀释剂:7-12%;Reactive diluent: 7-12%;
    助剂:2-3%;Auxiliary: 2-3%;
    颜料:11-14%;Pigment: 11-14%;
    陶瓷粉:20-34%。Ceramic powder: 20-34%.
  20. 根据权利要求19所述的环氧涂料层,其特征在于:所述助剂为润湿分散剂、防沉剂、消泡剂中的一种或几种的混合物;The epoxy coating layer according to claim 19, wherein the auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent;
    和/或,所述的双酚A环氧树脂的环氧当量为190液体环氧树脂;And/or, the bisphenol A epoxy resin has an epoxy equivalent of 190 liquid epoxy resin;
    和/或,所述的活性稀释剂为环氧当量为175-330的缩水甘油醚反应型活性稀释剂;And/or, the reactive diluent is a glycidyl ether reactive reactive diluent having an epoxy equivalent of 175-330;
    和/或,所述的颜料为金红石钛白粉和/或炭黑;And/or, the pigment is rutile titanium dioxide and/or carbon black;
    和/或,所述的陶瓷粉为石英粉或/和α-Al 2O 3And/or, the ceramic powder is quartz powder or/and α-Al 2 O 3 .
  21. 根据权利要求20所述的环氧涂料层,其特征在于:胺固化剂组分B包括:The epoxy coating layer according to claim 20, wherein the amine curing agent component B comprises:
    胺固化剂:22-30%;Amine curing agent: 22-30%;
    催化剂:0-2%Catalyst: 0-2%
    陶瓷粉:65-75%;Ceramic powder: 65-75%;
    助剂:3-4%。Additives: 3-4%.
  22. 根据权利要求21所述的环氧涂料层,其特征在于:The epoxy coating layer according to claim 21, wherein:
    所述催化剂为叔胺催化剂;The catalyst is a tertiary amine catalyst;
    和/或,助剂为润湿分散剂、防沉剂、消泡剂中的一种或几种的混合物。And/or the auxiliary agent is a mixture of one or more of a wetting and dispersing agent, an anti-settling agent, and an antifoaming agent.
    和/或,所述的陶瓷粉为石英粉或/和α-Al 2O 3And/or, the ceramic powder is quartz powder or/and α-Al 2 O 3 .
  23. 根据权利要求13所述的环氧涂料层,其特征在于:所述环氧陶瓷涂料层厚度为≥500μm,优选为500μm~2000μm,更优选为1000μm~1500μm。The epoxy coating layer according to claim 13, wherein the epoxy ceramic coating layer has a thickness of ≥ 500 μm, preferably 500 μm to 2000 μm, more preferably 1000 μm to 1500 μm.
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