CN111575629B - Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer - Google Patents
Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer Download PDFInfo
- Publication number
- CN111575629B CN111575629B CN202010421257.XA CN202010421257A CN111575629B CN 111575629 B CN111575629 B CN 111575629B CN 202010421257 A CN202010421257 A CN 202010421257A CN 111575629 B CN111575629 B CN 111575629B
- Authority
- CN
- China
- Prior art keywords
- layer
- corrosion
- amorphous alloy
- amorphous
- composite layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, 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 metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, 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
- B05D7/222—Processes, 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 of pipes
- B05D7/225—Coating inside the pipe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, 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
- B05D7/227—Processes, 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 of containers, cans or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
- C23C22/38—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention provides an anticorrosive composite layer, which sequentially comprises an amorphous alloy layer, an anticorrosive connecting layer and an acid-resistant ceramic layer, and also provides application of the anticorrosive composite layer as an anticorrosive composite lining layer of a pipeline or a container and a preparation method of the anticorrosive composite lining layer for the pipeline or the container. The anti-corrosion composite layer provided by the invention has a novel structure composition, is easy to form, firm and stable in combination, adjustable in thickness and excellent in corrosion resistance, has multiple protection effects on special working conditions in the fields of chemical engineering, metallurgy and the like, can be used as an inner liner of equipment such as pipelines and containers, and is particularly suitable for a process for producing alumina by using fly ash through a one-step acid dissolution method.
Description
Technical Field
The invention relates to the technical field of corrosion prevention, in particular to a corrosion-prevention composite layer, application thereof and a preparation method of a corrosion-prevention composite lining layer for a pipeline or a container.
Background
Shenhua quasi-energy resource comprehensive development Limited company fully utilizes the advantages of high aluminum and rich gallium in the quasi-Geer coal field, successfully develops a process technology for extracting metallurgical-grade alumina by a circulating fluidized bed fly ash one-step acid dissolution method in China, and the project has important significance for relieving the shortage of bauxite resources, ensuring the safety of aluminum industrial resources and the like.
In the harsh process stage of the one-step acid dissolution method, the working conditions of the inside of the container and the high-temperature end pipeline are severe, and the method mainly comprises the following steps: the working temperature is high (within the range of 150-180 ℃); the slurry is a non-oxidizing strong acid corrosion solution; a large number of solid particles exist, and have a certain high-temperature erosion effect on the lining. At present, aiming at the working conditions, the lining technology used in China mostly adopts a composite lining technology of 'shell-lining rubber-inorganic cement-acid-resistant brick', and the technology has the defects that the physical permeation resistance of an inorganic silicate adhesive is low, once a slurry solution has a multiphase flow high-temperature erosion effect on an inner lining interface, the slurry solution can permeate into a rubber layer from the inside of an inorganic colloid, the temperature resistance degree of the rubber layer is generally within the range of less than or equal to 120 ℃ (fluorine rubber is adopted), and at the moment, if the temperature gradient of the slurry solution in the permeation process is not less than 120 ℃, the rubber layer can generate the aging and damage phenomenon of high-temperature corrosion, so that the corrosive slurry solution is contacted with a metal shell to form local corrosive leakage.
Therefore, aiming at high-corrosiveness chemical and metallurgical processes such as a one-step acid dissolution process, a novel anticorrosion technology is urgently needed to be developed to ensure the safe, long-term and stable operation of equipment.
Disclosure of Invention
In order to overcome the aforementioned defects in the prior art, an object of the present invention is to provide an anticorrosive composite layer, which can be used in equipment in the fields of chemical industry, metallurgy, etc., especially equipment for highly corrosive processes, and has very excellent corrosion resistance.
Another object of the invention is to provide the use of the corrosion protection composite layer according to the invention.
It is still another object of the present invention to provide a method of making a corrosion resistant composite innerliner for a pipe or vessel.
The anti-corrosion composite layer provided by the invention sequentially comprises the following components:
an amorphous alloy layer having a thickness of 300 to 1000 μm and a material composition of a first amorphous alloy;
the anti-corrosion connecting layer is 50-300 mu m thick and comprises a phosphoric acid-copper oxide inorganic adhesive and an amorphous sheet filled in the phosphoric acid-copper oxide inorganic adhesive, and the amorphous sheet is made of a second amorphous alloy; and
the acid-resistant ceramic layer is 10-80 mm thick;
wherein the first amorphous alloy and the second amorphous alloy each independently have the following compositional composition: (Ni) 55～58 Ta 33～36 Sn 5～10 ) 100-x Er x And x represents an integer of 3 to 6 (specifically, x may represent 3, 4, 5 or 6).
The anti-corrosion composite layer has a novel structure and sequentially comprises three layers: the first amorphous alloy layer is an amorphous alloy layer, the first amorphous alloy used by the first amorphous alloy layer takes a nickel-based alloy as a base material, the addition amount of a rare earth element Er is correspondingly increased, the corrosion resistance of the obtained alloy is greatly improved, and the first amorphous alloy layer has obvious corrosion resistance to acid (such as hydrochloric acid) with higher concentration even at higher temperature; the second layer is an anticorrosive connecting layer, the adhesive material used by the second layer is phosphoric acid-copper oxide inorganic adhesive, and compared with the most commonly used inorganic rubber in the prior art, the adhesive has higher high-temperature resistance and acid corrosion resistance, so that the service life is longer, and the adhesive has higher compatibility with the amorphous thin sheet and the amorphous alloy layer after being bonded and cured, so that the combination of the anticorrosive composite layer is firmer and more stable; meanwhile, the adhesive material is also filled with an amorphous sheet of a second amorphous alloy, the second amorphous alloy also takes a nickel-based alloy as a base material, and a proper amount of rare earth element Er is added, so that the second amorphous alloy has excellent corrosion resistance, and the anticorrosive connecting layer filled with the amorphous sheet has good corrosion resistance, and due to the existence of the amorphous sheet, when corrosive fluid permeates into the anticorrosive connecting layer, the amorphous sheet can play a certain role in hindering the fluid to permeate in a tortuous manner, so that the thickness of the anticorrosive connecting layer is increased, the thickness of the anticorrosive connecting layer can be reduced when the anticorrosive connecting layer is arranged, and the phenomena of brittle cracking and the like caused by overlarge layer thickness are avoided; in addition, when thermal stress is generated, due to the flexible action of the amorphous thin sheet, the expansion of thermal cracks in the colloid can be greatly inhibited, so that the thermal shock damage resistance of the anti-corrosion composite layer is also improved; the third layer is an acid-resistant ceramic layer which forms an anticorrosive composite layer with excellent corrosion resistance together with the amorphous alloy layer and the anticorrosive connecting layer.
In the anti-corrosion composite layer of the present invention, the thickness of each layer can be properly adjusted or selected by those skilled in the art according to the application and actual working conditions. In a preferred embodiment, the thickness of the amorphous alloy layer may be 400 to 800 μm, for example, about 400 μm, about 500 μm, about 600 μm, about 700 μm, about 800 μm, and the like. In another preferred embodiment, the thickness of the corrosion resistant connecting layer may be 80 to 150 μm, for example, about 80 μm, about 90 μm, about 100 μm, about 110 μm, about 120 μm, about 130 μm, about 140 μm, about 150 μm, etc. In another preferred embodiment, the acid-resistant ceramic layer may have a thickness of 30 to 60mm, for example, about 30mm, about 40mm, about 50mm, about 60mm, etc.
In the anti-corrosion composite layer, the first amorphous alloy and the second amorphous alloy are nickel-based alloys containing Er element, and the components of the first amorphous alloy and the second amorphous alloy can be completely the same or have certain difference, so that the anti-corrosion composite layer has good anti-corrosion performance. In a preferred embodiment, both have the same composition and are made of the same master alloy, thereby reducing manufacturing costs and simplifying manufacturing processes.
In the anti-corrosion composite layer of the present invention, the first amorphous alloy and the second amorphous alloy may be prepared by methods known in the art, for example, each elemental metal with a purity of 99.99% is selected, and a master alloy is melted in a vacuum non-consumable arc furnace in a high purity argon atmosphere in which a titanium ingot absorbs oxygen, so that the prepared master alloy may be used to prepare an amorphous alloy layer and/or an amorphous sheet.
In the anticorrosive composite layer of the present invention, the preparation process of the amorphous alloy layer may include the following steps:
s1: preparing particles of the first amorphous alloy with the particle size of 20-40 mu m and forming the amorphous alloy layer through a plasma thermal spraying process; and
s2: brushing a phosphating solution on the surface of the amorphous alloy layer formed in the step S1 for phosphating treatment, wherein the phosphating solution is an aqueous solution with a pH value of 1.5-2.0 and comprises: cr (chromium) component 2 O 3 ：15～20g/L，H 3 PO 4 : 60-70 g/L and NaF: 6-10 g/L.
In the above step S1, the particles of the first amorphous alloy may be prepared by a method known in the art. In a preferred embodiment, the produced master alloy is made into particles by a nitrogen atomization process, which may include one or more of the following process conditions: the atomization pressure can be 8-10 MPa, the atomization temperature can be 1600-1800K, the mass-flow ratio is about 0.6, and the particles are screened into particles with the particle size of 20-40 mu m, and the micro morphology is mainly spherical and/or ellipsoidal.
In the step S1, the particles of the first amorphous alloy may be formed into the amorphous alloy layer by a plasma thermal spraying process. In the first amorphous alloy, the content of Er element is properly increased, and the proportion of other alloy elements is adjusted, so that the possibility of irreversible crystallization transformation of alloy particles in the thermal spraying process can be reduced, and the stability of the structure performance and the compactness of the internal structure of the amorphous alloy coating after spraying can be improved, and the corrosion resistance of the coating can be enhanced. As can be seen, the first amorphous alloy of the present invention has excellent thermal spraying properties, and the amorphous alloy layer can be formed by a plasma thermal spraying process.
The plasma thermal spray process used in step S1 above may include one or more of the following process conditions: the arc voltage can be 50-55V; the spraying current can be 500-550A; the main air flow can be 45-50L/min; the spraying distance can be 120-150 mm; the powder feeding amount can be 2-2.5 kg/h; the thickness of each spraying can be 100-200 mu m, and the thickness of the amorphous alloy layer is reached after 3-5 times of spraying; the specific conditions of the thermal spraying process can be adjusted or selected by those skilled in the art according to the composition, application, actual conditions, etc. of the first amorphous alloy. In a preferred embodiment, compressed air may be used for cooling between each spray; more preferably, compressed air may be used for continuous cooling between each spray application, and the inside diameter of the air may be
The pressure intensity can be 0.8-1 MPa.
In the step S2, the surface of the amorphous alloy coating layer can be soaked in the phosphating solution by performing phosphating on the surface of the formed amorphous alloy layer, so as to form a certain amorphous film structure with a microscopic phase, and the dissociated phosphate radical in the film structure can be combined with the anti-corrosion connecting layer, thereby forming a firmer bonding interface, so that the coating layer and the anti-corrosion connecting layer have stronger adhesiveness, and the bonding strength of the composite layer is greatly improved.
In the step S2, the number of brush coating passes of the phosphating solution may be 3 to 6, and the interval time between each brush coating pass may be 10 to 30 min.
In the anticorrosive composite layer, the width of the amorphous sheet can be 2-3 mm, the thickness can be 30-50 mu m, and the length can be 0.5-1 mm; the amorphous flakes may be prepared by a method known in the art, for example, by placing a mother alloy of a second amorphous alloy after ultrasonic cleaning in a quartz tube having a small hole at the bottom, remelting on a vacuum strip thrower using an induction heating device, and blowing the molten alloy onto the surface of a copper roll rotating at high speed with high-pressure argon gas, thereby obtaining a thin strip sample, and then crushing the length of the thin strip sample to a desired length with a paper scrap crusher.
In the anticorrosive composite layer of the invention, the weight ratio of the phosphoric acid-copper oxide inorganic adhesive to the amorphous sheet may be 10: 0.1 to 1, and the specific weight ratio can be adjusted or selected by those skilled in the art according to the application and actual conditions. In a preferred embodiment, the weight ratio of the phosphoric acid-copper oxide inorganic binder to the amorphous flakes may be 10: 0.3 to 0.8, for example, can be about 10: 0.3, about 10: 0.4, about 10: 0.5, about 10: 0.6, about 10: 0.7, about 10: 0.8, etc.
In the anticorrosive composite layer of the invention, the preparation process of the anticorrosive connecting layer comprises the following steps: and uniformly mixing the phosphoric acid-copper oxide inorganic adhesive with the amorphous sheet, and coating the obtained mixed material on the amorphous alloy layer to form the anticorrosive connecting layer.
In the anticorrosive composite layer of the present invention, the preparation process of the acid-resistant ceramic layer includes bonding the acid-resistant ceramic to the anticorrosive connecting layer, and the acid-resistant ceramic used in the anticorrosive composite layer of the present invention may be a kind commonly used in the art. In a preferred embodiment, the acid-resistant ceramic may be a silicate-based acid-resistant ceramic.
The invention also provides application of the anti-corrosion composite layer in any one of the technical schemes as an anti-corrosion composite lining layer of a pipeline or a container, wherein the amorphous alloy layer in the anti-corrosion composite layer is connected with the inner surface of the pipeline or the container.
The anti-corrosion composite layer provided by the invention has a firm and stable structure with proper thickness and excellent anti-corrosion performance, and can meet the anti-corrosion requirements of equipment in the fields of chemical engineering, metallurgy and the like, such as pipeline or reaction tank, material tank, mixing tank and other container equipment, and is especially suitable for process equipment with harsh working conditions (such as high temperature, high corrosivity and the like). In a preferred embodiment, the pipe or vessel is a pipe or vessel in a fly ash "one-step acid solution process" for producing alumina.
The invention also provides a preparation method of the anti-corrosion composite lining layer for the pipeline or the container, which takes the inner surface of the pipeline or the container as a substrate, and the anti-corrosion composite layer in any one of the technical schemes is formed on the inner surface of the pipeline or the container, wherein the amorphous alloy layer in the anti-corrosion composite layer is connected with the substrate.
In a preferred embodiment, the pipe or vessel is a pipe or vessel in a fly ash "one-step acid solution process" for producing alumina.
In the preparation method provided by the invention, before the anti-corrosion composite layer is formed, the following pretreatment processes can be carried out on the substrate: cleaning with a mixed aqueous solution containing 5-15 wt% of sodium hydroxide and 5-15 wt% of sodium tripolyphosphate; and
using diamond sand grains with the grain size of 30-50 μm to perform sand blasting roughening treatment at an incident angle of 30-70 degrees.
The technical scheme provided by the invention has the following advantages:
(1) compared with the existing anticorrosion lining structure, the anticorrosion composite layer provided by the invention comprises the amorphous alloy layer, the anticorrosion connecting layer and the acid-resistant ceramic layer, has a novel structural composition, and is easy to form, firm and stable in combination and adjustable in thickness.
(2) The anti-corrosion composite layer has excellent corrosion resistance, has multiple protection effects on special working conditions in the fields of chemical engineering, metallurgy and the like, can be used as an inner liner of equipment such as pipelines and containers, effectively solves the problem of local tolerance of the inner liner of the equipment to harsh working conditions such as high-temperature aging, acid corrosion, multiphase flow erosion and the like, is particularly suitable for the process for producing alumina by using fly ash through a one-step acid dissolution method, and can ensure safe, stable and long-time operation of process production.
(3) The preparation method of the anti-corrosion composite inner liner layer is simple and convenient in process, does not need complex devices and high cost, and has practical application value.
Drawings
FIG. 1 is an image of an anti-corrosive composite layer of the present invention in various manufacturing steps; wherein, a) is a scanning electron microscope image of the amorphous alloy powder after the atomization process, b) is a scanning electron microscope image of the longitudinal section of the coating after the amorphous alloy layer is formed (after phosphating treatment), c) is an optical micrograph of the surface of the amorphous alloy layer after phosphating treatment, and d) is a scanning electron microscope image of the longitudinal section of the composite layer after the anti-corrosion connecting layer is formed;
in the above figures, the layer A is an amorphous alloy layer, and the layer B is an anti-corrosion connecting layer.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The sources of the reagents, raw materials and equipment used in the examples and comparative examples of the present invention are shown in tables 1 and 2.
TABLE 1
TABLE 2
Other raw materials and/or equipment for reagents were commercially available products unless otherwise specified.
The percentages used in the examples according to the invention and in the comparative examples are, unless otherwise specified, all percentages by mass.
Example 1
The composition of the amorphous alloy used in this example was (Ni) 58 Ta 34 Sn 8 ) 97 Er 3 And selecting each elementary metal with the purity of 99.99% to carry out master alloy smelting in a high-purity argon environment for oxygen absorption of a titanium ingot of a vacuum non-consumable electric arc furnace, wherein the obtained master alloy is used for preparing amorphous alloy powder and amorphous slices.
(1) Preparation of amorphous alloy powder
And (2) preparing the mother alloy into amorphous alloy powder by a nitrogen atomization process, wherein the atomization pressure is 10MPa, the atomization temperature is 1600K, the mass-flow ratio is about 0.6, and the amorphous alloy powder with the granularity of 25-30 mu m and spherical and ellipsoidal micro-morphology is further screened.
(2) Preparation of amorphous flakes
The method comprises the steps of cleaning a master alloy by ultrasonic waves, then placing the cleaned master alloy into a quartz tube with a small hole at the bottom, remelting the master alloy on a vacuum strip throwing machine by using an induction heating device, blowing the molten alloy onto the surface of a copper roller rotating at a high speed by using high-pressure argon to obtain a thin strip sample with the width of 2-3 mm and the thickness of 40-45 mu m, and crushing the length of the thin strip sample to 0.5-0.8 mm by using a paper scrap crusher.
(3) Preparation of anticorrosive composite inner liner
The method comprises the steps of taking a high-temperature dissolution pipeline (made of carbon steel) used for a one-step acid dissolution process as a substrate, cleaning the inner surface of the pipeline by adopting a mixed solution of 10% of sodium hydroxide and 10% of sodium tripolyphosphate, and then carrying out sand blasting coarsening treatment on angular diamond sand grains with the grain size of 30-40 microns at an incidence angle of 30-50 degrees.
Spraying the prepared amorphous alloy powder on the treated inner surface to prepare a first amorphous alloy layer, wherein the coating adopts plasma thermal spraying, and the specific process conditions are as follows: an arc voltage 54A; spraying current 530V; the main gas flow is 45L/min; the spraying distance is 130 mm; the powder feeding amount is 2.5 kg/h; the thickness of each coating is 120 mu m, the coating reaches 500 mu m after 5 times of spraying, the compressed air is adopted to rapidly cool each coating in the middle, the compressed air is adopted to continuously cool the surface of the coating, and the inner diameter of the air is
The pressure is 0.8 MPa.
Carrying out phosphating treatment on the surface of the prepared amorphous alloy layer, wherein the phosphating treatment adopts a brush coating mode, and the phosphating solution comprises the following components: cr 2 O 3 ：20g/L；H 3 PO 4 : 60 g/L; NaF: 6 g/L; pH: 1.5; brushing for times: 4 times; interval time of each pass: and (5) 20 min.
Mixing and filling the prepared amorphous slices in a phosphoric acid-copper oxide inorganic adhesive; inorganic adhesive: amorphous flakes (by mass ratio) 10: 0.5. and then coating the inorganic adhesive filled with the amorphous slices on the phosphatized amorphous alloy layer to form an anticorrosive connecting layer, wherein the thickness of the connecting layer is about 100 mu m.
And finally, bonding a layer of acid-resistant ceramic on the anti-corrosion connecting layer to form an acid-resistant ceramic layer, thereby forming the anti-corrosion composite lining layer.
The b) and d) in fig. 1 are the micro-morphology of the amorphous alloy layer, and it can be seen that the amorphous phase in the coating layer is generated, and a certain amorphous film structure with the micro-phase is formed.
Example 2
The composition of the amorphous alloy used in this example was (Ni) 55 Ta 35 Sn 10 ) 96 Er 4 The melting was carried out in the same manner as in example 1 to obtain a master alloy.
(1) Preparation of amorphous alloy powder
The master alloy is made into amorphous alloy powder through a nitrogen atomization process, the atomization pressure is 8MPa, the atomization temperature is 1800K, the mass-flow ratio is about 0.6, and the amorphous alloy powder with the granularity of 30-40 mu m and spherical and ellipsoidal micro-morphology is further sieved.
(2) Preparation of amorphous flakes
The method comprises the steps of cleaning a master alloy through ultrasonic waves, then placing the cleaned master alloy into a quartz tube with a small hole at the bottom, remelting the master alloy on a vacuum strip throwing machine through an induction heating device, blowing the molten alloy onto the surface of a copper roller rotating at a high speed through high-pressure argon to obtain a thin strip sample with the width of 2-3 mm and the thickness of 30-45 micrometers, and crushing the length of the thin strip sample to 0.5-1 mm through a paper scrap crusher.
(3) Preparation of anticorrosive composite inner liner
The method comprises the steps of taking a high-temperature dissolution pipeline (made of carbon steel) used for a one-step acid dissolution process as a substrate, cleaning the inner surface of the pipeline by adopting a mixed solution of 10% of sodium hydroxide and 10% of sodium tripolyphosphate, and then carrying out sand blasting coarsening treatment on diamond sand particles with edges and corners and with the particle size of 40-50 microns at an incidence angle of 40-70 degrees.
The amorphous alloy powder is sprayed on the treated inner surface to prepare a first amorphous alloy layer, the coating adopts plasma thermal spraying, and the specific process conditions are as follows: arc voltage 53V; spraying current 550A; the main gas flow is 50L/min; the spraying distance is 130 mm; powder feeding amount of 2kgH; the thickness of each coating is 100 mu m, the coating reaches 500 mu m after 5 times of spraying, the compressed air is adopted to carry out rapid cooling on each coating in the middle, the compressed air is adopted to carry out continuous cooling on the surface of the coating, and the inner diameter of the air is
The pressure is 1 MPa.
Carrying out phosphating treatment on the surface of the prepared amorphous alloy layer, wherein the phosphating treatment adopts a brush coating mode, and the phosphating solution comprises the following components: cr (chromium) component 2 O 3 ：15g/L；H 3 PO 4 : 70 g/L; NaF: 10 g/L; pH: 2.0; brushing for times: 3 times of treatment; interval time of each pass: and (5) 30 min.
Mixing and filling the prepared amorphous slices in a phosphoric acid-copper oxide inorganic adhesive; phosphoric acid-copper oxide inorganic adhesive the inorganic adhesive: amorphous flakes (by mass ratio) 10: 0.5; and then coating the inorganic adhesive filled with the amorphous slices on the phosphated amorphous alloy coating to form an anticorrosive connecting layer, wherein the thickness of the layer is about 120 mu m.
And finally, bonding a layer of acid-resistant ceramic on the anti-corrosion connecting layer to form an acid-resistant ceramic layer, thereby forming the anti-corrosion composite lining layer.
Example 3
The composition of the amorphous alloy used in this example was (Ni) 57 Ta 34 Sn 9 ) 94 Er 6 Smelting was carried out in the same manner as in example 1 to obtain a master alloy.
(1) Preparation of amorphous alloy powder
And (2) preparing the mother alloy into amorphous alloy powder by a nitrogen atomization process, wherein the atomization pressure is 9MPa, the atomization temperature is 1700K, the mass-flow ratio is about 0.6, and the amorphous alloy powder with the granularity of 30-40 mu m and spherical and ellipsoidal micro-morphology is further screened.
(2) Preparation of amorphous flakes
The method comprises the steps of cleaning a master alloy by ultrasonic waves, then placing the cleaned master alloy into a quartz tube with a small hole at the bottom, remelting the master alloy on a vacuum strip throwing machine by using an induction heating device, blowing the molten alloy onto the surface of a copper roller rotating at a high speed by using high-pressure argon to obtain a thin strip sample with the width of 2-3 mm and the thickness of 35-45 mu m, and crushing the length of the thin strip sample to 0.5-1 mm by using a paper scrap crusher.
(3) Preparation of anticorrosive composite inner liner
The method comprises the steps of taking a high-temperature dissolution pipeline (made of carbon steel) used for a one-step acid dissolution process as a substrate, cleaning the inner surface of the pipeline by adopting a mixed solution of 10% of sodium hydroxide and 10% of sodium tripolyphosphate, and then carrying out sand blasting coarsening treatment on angular diamond sand grains with the grain size of 35-45 mu m at an incidence angle of 40-60 degrees.
The amorphous alloy powder is sprayed on the treated inner surface to prepare a first amorphous alloy layer, the coating adopts plasma thermal spraying, and the specific process conditions are as follows: arc voltage 54V; spraying current 540A; the main gas flow is 50L/min; the spraying distance is 130 mm; the powder feeding amount is 2.2 kg/h; the thickness of each coating is 150 mu m, the required specified coating thickness is 500 mu m after 4 times of spraying, the rapid cooling of each coating is carried out by adopting compressed air in the middle, the surface of the coating is continuously cooled by adopting the compressed air, and the inner diameter of the air is
The pressure was 0.9 MPa.
The surface of the prepared amorphous alloy coating is subjected to phosphating treatment in a brush coating mode, and phosphating solution comprises the following components: cr (chromium) component 2 O 3 ：15g/L；H 3 PO 4 : 65 g/L; NaF: 8 g/L; pH: 2.0 of the total weight of the mixture; brushing for times: 4 times of treatment; interval time of each pass: and 20 min.
Mixing and filling the prepared amorphous slices in a phosphoric acid-copper oxide inorganic adhesive; phosphoric acid-copper oxide inorganic adhesive: amorphous flakes (by mass ratio) 10: 0.5; and then coating the inorganic adhesive filled with the amorphous slices on the phosphated amorphous alloy coating to form an anticorrosive connecting layer, wherein the thickness of the layer is about 130 mu m.
And finally, bonding a layer of acid-resistant ceramic on the anti-corrosion connecting layer to form an acid-resistant ceramic layer, thereby forming the anti-corrosion composite lining layer.
Comparative example 1
A single amorphous alloy coating (i.e., excluding the corrosion resistant joint layer and the acid resistant ceramic layer) was formed in the carbon steel digestion pipe in the same manner as in example 2.
Comparative example 2
An anticorrosive composite inner liner was formed in a carbon steel pipeline in the same manner as in example 2, except that the amorphous alloy layer was not phosphatized.
Test example
The weight of the dissolution tubing at different run times was tested according to the following procedure:
the dissolution pipeline containing the inner liner obtained in each example and comparative example is cut into square samples and marked with weight, each sample is washed by distilled water and ethanol, dried in an oven at a constant temperature of 60 ℃ for 24 hours, then fixed on the inner wall of a polytetrafluoroethylene cup in a plastic package mode, then a container is filled with slurry solution (consisting of hydrochloric acid solution with the weight percent of about 25 percent and fly ash with the concentration of about 40 percent by weight), the polytetrafluoroethylene cup is placed in a high temperature reaction kettle (HTD8040D), the stirring speed of the cup is set to be 2m/s, the temperature of the cup is set to be 110 ℃, and the test is started. And stopping the test after the test days meet the specified requirements, taking down the test sample, washing the test sample by using distilled water and ethanol respectively, drying the test sample in an oven at constant temperature, weighing the test sample, recording the final weight of the test sample, and obtaining the final result shown in the table 3.
TABLE 3 results of elution tubing quality as a function of run time
Table 3 shows the weights of the pipe samples containing the inner liner obtained in each example and comparative example at different running times, and the corrosive consumption of the inner shell and the inner liner of the pipe by the slurry solution transported in the pipe resulted in the decrease in the quality of the samples, which reflects the corrosion resistance of the inner liner. As can be seen from Table 3, compared with comparative example 1 (single amorphous alloy coating) and comparative example 2 (no phosphating treatment), the corrosion weight loss values of examples 1 to 3 are smaller, which shows that the anticorrosive composite inner liners of examples 1 to 3 have better corrosion resistance and relatively longer service life under actual working conditions.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (16)
1. An anti-corrosion composite layer is characterized by sequentially comprising the following components:
an amorphous alloy layer having a thickness of 300 to 1000 μm and a material composition of a first amorphous alloy;
the anti-corrosion connecting layer is 50-300 mu m thick and comprises a phosphoric acid-copper oxide inorganic adhesive and an amorphous sheet filled in the phosphoric acid-copper oxide inorganic adhesive, and the amorphous sheet is made of a second amorphous alloy; and
the acid-proof ceramic layer is 10-80 mm thick;
wherein the first amorphous alloy and the second amorphous alloy each independently have the following composition: (Ni) 55～ 58 Ta 33～36 Sn 5～10 ) 100-x Er x And x represents an integer of 3 to 6.
2. The corrosion-resistant composite layer according to claim 1, wherein the thickness of the amorphous alloy layer is 400 to 800 μm; and/or
The thickness of the anti-corrosion connecting layer is 80-150 micrometers; and/or
The thickness of the acid-proof ceramic layer is 30-60 mm; and/or
The first amorphous alloy and the second amorphous alloy have the same composition.
3. The corrosion-resistant composite layer according to claim 1 or 2, wherein the preparation process of the amorphous alloy layer comprises the following steps:
s1: preparing particles of the first amorphous alloy with the particle size of 20-40 mu m and forming the amorphous alloy layer through a plasma thermal spraying process; and
s2: brushing a phosphating solution on the surface of the amorphous alloy layer formed in the step S1 to perform phosphating treatment, wherein the phosphating solution is an aqueous solution with the pH value of 1.5-2.0 and comprises: cr 2 O 3 ：15～20g/L，H 3 PO 4 : 60-70 g/L and NaF: 6-10 g/L.
4. The anti-corrosion composite layer according to claim 3, wherein the phosphating solution is coated for 3 to 6 times at intervals of 10 to 30 min.
5. The anti-corrosion composite layer according to claim 3, wherein the plasma thermal spraying process in the step S1 includes one or more of the following process conditions: the arc voltage is 50-55V; the spraying current is 500-550A; the main gas flow is 45-50L/min; the spraying distance is 120-150 mm; the powder feeding amount is 2-2.5 kg/h; the thickness of each spraying is 100-200 mu m, and the thickness of the amorphous alloy layer is achieved after 3-5 times of spraying.
6. An anti-corrosive composite layer according to claim 5, wherein compressed air is used for cooling between each spraying.
7. The anticorrosion composite layer as set forth in claim 1 or 2, wherein the amorphous sheet has a width of 2 to 3mm, a thickness of 30 to 50 μm, and a length of 0.5 to 1 mm; the weight ratio of the phosphoric acid-copper oxide inorganic adhesive to the amorphous flakes is 10: 0.1 to 1.
8. The anticorrosive composite layer of claim 7, wherein the weight ratio of the inorganic phosphoric acid-copper oxide adhesive to the amorphous flakes is 10: 0.3 to 0.8.
9. An anti-corrosion composite layer according to claim 7, wherein the preparation process of the anti-corrosion connecting layer comprises: and uniformly mixing the phosphoric acid-copper oxide inorganic adhesive with the amorphous sheet, and coating the obtained mixed material on the amorphous alloy layer to form the anticorrosive connecting layer.
10. Anti-corrosion composite layer according to claim 1 or 2, wherein the preparation of the acid-resistant ceramic layer comprises bonding an acid-resistant ceramic to the anti-corrosion connecting layer.
11. The corrosion resistant composite layer as recited in claim 10 wherein said acid resistant ceramic is a silicate acid resistant ceramic.
12. Use of an anti-corrosive composite layer according to any one of claims 1 to 11 as an anti-corrosive composite inner liner for a pipe or a vessel, wherein the amorphous alloy layer in the anti-corrosive composite layer is attached to the inner surface of the pipe or vessel.
13. Use according to claim 12, wherein the pipe or vessel is a pipe or vessel in a fly ash "one-step acid solution process" for producing alumina.
14. A method for preparing an anti-corrosion composite lining layer for a pipeline or a container, which is characterized in that the inner surface of the pipeline or the container is taken as a substrate, and the anti-corrosion composite layer as claimed in any one of claims 1 to 11 is formed on the inner surface, wherein an amorphous alloy layer in the anti-corrosion composite layer is connected with the substrate.
15. The method for preparing the alumina powder of the claim 14, wherein the pipeline or the container is a pipeline or a container in a process for producing alumina by using fly ash through a one-step acid dissolution method.
16. A production method according to claim 14 or 15, characterized in that, before forming the corrosion-preventing composite layer, the substrate is subjected to the following pretreatment process: cleaning with a mixed aqueous solution containing 5-15 wt% of sodium hydroxide and 5-15 wt% of sodium tripolyphosphate; and
carrying out sand blasting coarsening treatment on diamond sand grains with the grain size of 30-50 mu m at an incident angle of 30-70 degrees.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010421257.XA CN111575629B (en) | 2020-05-18 | 2020-05-18 | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010421257.XA CN111575629B (en) | 2020-05-18 | 2020-05-18 | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111575629A CN111575629A (en) | 2020-08-25 |
| CN111575629B true CN111575629B (en) | 2022-07-26 |
Family
ID=72126832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010421257.XA Active CN111575629B (en) | 2020-05-18 | 2020-05-18 | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111575629B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388799B (en) * | 2021-05-14 | 2022-07-26 | 中山市明焱诚铝业有限公司 | Preparation method of corrosion-resistant aluminum alloy |
| CN115181968B (en) * | 2021-09-08 | 2023-06-16 | 武汉苏泊尔炊具有限公司 | Container and method for manufacturing the same |
| CN114633044B (en) * | 2022-03-31 | 2024-05-24 | 神华准能资源综合开发有限公司 | Solder for brazing ceramic lining and stainless steel and brazing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010008577A2 (en) * | 2008-07-17 | 2010-01-21 | C3 International, Llc | Methods for protecting exterior surfaces from corrosion, biofouling, and particulate erosion |
| CN103738003A (en) * | 2013-12-27 | 2014-04-23 | 中国神华能源股份有限公司 | Composite lining for corrosion prevention of dissolution tank |
| CN103898422A (en) * | 2014-03-07 | 2014-07-02 | 北京理工大学 | Al-Ni-Er series aluminum-based amorphous alloy material and preparation method thereof |
| CN109580467A (en) * | 2018-12-17 | 2019-04-05 | 中国神华能源股份有限公司 | A kind of test equipment and test method of resistant material corrosion life |
| CN110004350A (en) * | 2019-04-15 | 2019-07-12 | 烟台奥泰新材料有限公司 | A kind of amorphous Stainless steel application powder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60209295T2 (en) * | 2002-12-30 | 2006-11-02 | Shin-Etsu Chemical Co., Ltd. | Heat-resistant coated element |
| US10465285B2 (en) * | 2016-05-31 | 2019-11-05 | Goodrich Corporation | High temperature oxidation protection for composites |
-
2020
- 2020-05-18 CN CN202010421257.XA patent/CN111575629B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010008577A2 (en) * | 2008-07-17 | 2010-01-21 | C3 International, Llc | Methods for protecting exterior surfaces from corrosion, biofouling, and particulate erosion |
| CN103738003A (en) * | 2013-12-27 | 2014-04-23 | 中国神华能源股份有限公司 | Composite lining for corrosion prevention of dissolution tank |
| CN103898422A (en) * | 2014-03-07 | 2014-07-02 | 北京理工大学 | Al-Ni-Er series aluminum-based amorphous alloy material and preparation method thereof |
| CN109580467A (en) * | 2018-12-17 | 2019-04-05 | 中国神华能源股份有限公司 | A kind of test equipment and test method of resistant material corrosion life |
| CN110004350A (en) * | 2019-04-15 | 2019-07-12 | 烟台奥泰新材料有限公司 | A kind of amorphous Stainless steel application powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111575629A (en) | 2020-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111575629B (en) | Anti-corrosion composite layer, application and preparation method of anti-corrosion composite lining layer | |
| CN114226722B (en) | Corrosion-resistant material, corrosion-resistant layer prepared therefrom, and cooker comprising corrosion-resistant layer | |
| CN109972070B (en) | Metal composite material with protective coating coated on surface and preparation process thereof | |
| CN102400001B (en) | Method for preparing granule reinforced aluminum-based composite material of in-situ intermetallic compound | |
| CN110396687A (en) | A kind of Ti2AlC MAX phase ceramics coating and its cold spraying preparation method | |
| CN113105115A (en) | High-temperature-resistant enamel-based composite coating with self-repairing function and preparation method thereof | |
| CN112209727A (en) | Ceramic coating for heating surface of power plant boiler and preparation method thereof | |
| JP5528559B2 (en) | Pretreatment method for enhancing oxidation resistance of T91 / P91 steel in high temperature steam | |
| CN1451696A (en) | High-temp. resistant wear-preventing paint | |
| CN112457061A (en) | Environment barrier coating with gradient change of components and preparation method thereof | |
| CN112626442A (en) | High-temperature oxidation-resistant and corrosion-resistant coating and preparation method thereof | |
| CN115108820B (en) | Preparation method of high-temperature-resistant wear-resistant ceramic coating | |
| CN117305748A (en) | High-temperature self-lubricating abradable seal coating and preparation method thereof | |
| CN107904536B (en) | Sealant-free molten zinc-aluminum corrosion resistant coating material and preparation method thereof | |
| CN111943707B (en) | Adhesive for mullite ceramic tube and preparation method and application method thereof | |
| CN101774019B (en) | Metal/nanometer zirconia composite spherical powder material used for gradient coating and preparation method thereof | |
| CN110484907A (en) | A kind of composite material | |
| CN108707897B (en) | Ceramic coating of exhaust pipe and preparation method thereof | |
| CN111217613A (en) | Magnesium-calcium material and preparation method thereof | |
| CN108588710B (en) | Preparation method of nickel-based alloy coating for cold coating medium-frequency induction cladding and composite auxiliary agent | |
| CN110698065A (en) | Steel pipe with glass lining | |
| CN110699685A (en) | Method for producing composite material | |
| CN117587350B (en) | Corrosion-resistant anti-adhesion aluminum-based seal coating material and preparation method thereof | |
| CN116162931B (en) | Bottom blowing spray gun composite coating, preparation method thereof and bottom blowing spray gun | |
| CN107573972B (en) | Anticorrosion and wear-resistant treatment method for Lurgi gasification furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |