A repair material for a spillway structure and a method of manufacturing the same

Abstract

The application belongs to the technical field of water conservancy and hydropower engineering, and discloses a repairing material for a water discharge structure and a preparation method thereof. The repairing material comprises cement, aggregate, water and a colorant. The proportioning of the cement, the aggregate, the water and the colorant is adjusted according to engineering requirements. The colorant comprises arsenic-molybdenum hybrid polyacid salt, potassium cobalt trioxalate and cobalt ammonium phosphate. The repairing material meets the performance requirements of the water discharge structure after concrete repair. On this basis, the repairing material can effectively cover up the concrete repair traces of the water discharge structure and improve the aesthetic appearance of the water discharge structure. In addition, the repairing material can gradually change the color of the repaired part through heating and xenon lamp irradiation, so that the amount of the colorant to be added is not required to be found through multiple tests, thereby saving time and materials.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water conservancy and hydropower engineering, and particularly relates to a repair material for a water discharge structure and a preparation method thereof. BACKGROUND

[0002] During the service process, the water discharge structure is affected by environmental factors to cause various diseases, especially the problems of sand abrasion and cavitation erosion, which seriously affect the safety of the power station and the power generation benefit and seriously affect the service life of the project. In order to ensure the safe operation of the subsequent structure, the structure needs to be repaired according to the damage situation.

[0003] However, due to the factors such as the erosion of sulfate and the aging of ultraviolet radiation, the color of the concrete of the water discharge structure will change to some extent, and the color of the selected repair material is also different from that of the concrete of the water discharge structure. The current concrete repair material does not consider the unity and coordination of the appearance of the water discharge structure, which leads to many large and small "psoriasis" after the repair of the water discharge structure, which is extremely unsightly and destroys the landscape value and tourism value of the water conservancy hub.

[0004] Therefore, in order to achieve the effect of "repairing the old as the old" in the sense, without affecting the repair performance of the water discharge structure, it is of great significance to develop a new type of concrete repair material for the water discharge structure to improve the repair effect of the water discharge structure. SUMMARY

[0005] In order to overcome the defects of the prior art, the purpose of the present application is to provide a repair material for the concrete of the water discharge structure and a preparation method thereof, so as to improve the aesthetic degree of the concrete of the water discharge structure after repair.

[0006] The first purpose of the present application is to provide a repair material for a water discharge structure, which comprises cement, aggregate, water and a coloring agent.

[0007] The proportion of cement, aggregate, water and coloring agent is adjusted according to engineering needs.

[0008] The coloring agent comprises arsenic molybdenum hybrid polyacid salt, potassium cobalt trioxalate and cobalt ammonium phosphate.

[0009] Further, the coloring agent comprises 50% arsenic molybdenum hybrid polyacid salt, 25% potassium cobalt trioxalate and 25% cobalt ammonium phosphate by mass percentage.

[0010] The second purpose of the present application is to provide a preparation method of the repair material for the water discharge structure, which comprises:

[0011] The coloring agent is prepared by using arsenic molybdenum hybrid polyacid salt, potassium cobalt trioxalate and cobalt ammonium phosphate.

[0012] Cement and aggregate are mixed according to a preset ratio, and water in which a colorant is dissolved is added during the mixing process to obtain concrete mixture;

[0013] The concrete mixture is poured into a mold, vibrated and compacted, placed in a curing box for curing, and finally demolded to obtain a demolded material;

[0014] The demolded material is heated and irradiated with a xenon lamp in sequence to adjust the color of the demolded material, thereby obtaining a target-color repair material.

[0015] Further, the method for preparing the arsenic-molybdenum hybrid polyacid salt comprises:

[0016] Ammonium molybdate is dissolved in water to obtain an ammonium molybdate aqueous solution;

[0017] The ammonium molybdate aqueous solution is stirred and As2O3, NaOH, CsCl and 5-hydroxy-1,3-benzenedicarboxylic acid are added to obtain a mixed solution;

[0018] The mixed solution is heated under reflux at a temperature of 90-95°C, and then left to cool to room temperature;

[0019] The cooled mixed solution is filtered and left to volatilize, thereby obtaining colorless and transparent arsenic-molybdenum hybrid polyacid salt crystals.

[0020] Further, when preparing the arsenic-molybdenum hybrid polyacid salt, the mass ratio of water, ammonium molybdate, As2O3, NaOH, CsCl and 5-hydroxy-1,3-benzenedicarboxylic acid is 15:0.53:0.05:0.06:0.10:0.14.

[0021] Further, the method for preparing potassium cobalt trioxalate comprises:

[0022] Oxalic acid and potassium oxalate are added to water and stirred and dissolved at 60°C, and then cobalt carbonate powder is added to obtain a first mixed solution;

[0023] The temperature of the first mixed solution is lowered to 35°C, and then lead dioxide and anhydrous acetic acid solution are added and stirred to obtain a second mixed solution;

[0024] The second mixed solution is left to cool and suction-filtered to obtain a filtrate;

[0025] Anhydrous ethanol is added to the filtrate to precipitate a crystalline substance;

[0026] The filtrate with the precipitated crystalline substance is filtered and dried to obtain potassium cobalt trioxalate.

[0027] Further, when preparing potassium cobalt trioxalate, the ratio of water, oxalic acid, potassium oxalate, cobalt carbonate, lead dioxide, anhydrous acetic acid and anhydrous ethanol is 250 mL:0.1 mol:0.2 mol:0.1 mol:0.2 mol:250 mL.

[0028] Further, the drying temperature is 80℃ when preparing the potassium cobalt trioxalate.

[0029] Further, the preparation method of the ammonium cobalt phosphate comprises:

[0030] The cobalt chloride hexahydrate aqueous solution is prepared according to the molar volume ratio of 0.5 mol / L;

[0031] The diammonium hydrogen phosphate is mixed with the deionized water according to the molar volume ratio of 5 mol / L, and stirred to obtain a supersaturated diammonium hydrogen phosphate solution;

[0032] The cobalt chloride hexahydrate aqueous solution and the supersaturated diammonium hydrogen phosphate solution are mixed and stirred at room temperature according to the volume ratio of 1:1, and after standing and aging, the supernatant is removed to obtain a lower turbid liquid;

[0033] The lower turbid liquid is washed with deionized water for multiple times and filtered, and then dried to obtain the ammonium cobalt phosphate.

[0034] Further, the drying temperature is 85℃ when preparing the ammonium cobalt phosphate.

[0035] Technical effects and advantages of the present application:

[0036] 1. The repair material of the present application meets the performance requirements of the repaired concrete of the water discharge structure, and on this basis, can effectively cover the repair marks of the concrete of the water discharge structure, and improve the aesthetic degree of the water discharge structure.

[0037] 2. The repair material of the present application can gradually change the color of the repaired part by heating and xenon lamp irradiation, and does not need to test the amount of coloring material multiple times, saving time and materials.

[0038] Other features and advantages of the present application will be described in the subsequent description, and some will become apparent from the description, or will be understood by those skilled in the art through implementation of the present application. The purpose and other advantages of the present application can be achieved and obtained through the structure indicated in the specification, claims and drawings. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 It is a preparation method flow chart of the repair material of the concrete of the water discharge structure of the present application. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0041] In a first aspect, the present application provides a repairing material for a spillway structure, the repairing material comprising cement, aggregate, water, and a colorant;

[0042] The cement, the aggregate, the water, and the colorant are adjusted according to engineering requirements.

[0043] The colorant comprises arsenic-molybdenum hybrid polyacid salt, potassium cobalt trioxalate, and cobalt ammonium phosphate.

[0044] In some embodiments of the present application, the colorant comprises, by mass percentage, 50% arsenic-molybdenum hybrid polyacid salt, 25% potassium cobalt trioxalate, and 25% cobalt ammonium phosphate.

[0045] In a second aspect, as shown in Figure 1 The present application discloses a preparation method of a repairing material for a spillway structure, comprising:

[0046] The colorant is prepared using arsenic-molybdenum hybrid polyacid salt, potassium cobalt trioxalate, and cobalt ammonium phosphate.

[0047] The cement and the aggregate are mixed according to a preset ratio, and water in which the colorant is dissolved is added during the mixing process to obtain a concrete mixture;

[0048] The concrete mixture is poured into a mold, vibrated and compacted, placed in a curing box for curing, and finally demolded to obtain a demolding material;

[0049] The demolding material is sequentially heated and irradiated with a xenon lamp to adjust the color of the demolding material, and a repairing material of a target color is obtained.

[0050] In some embodiments of the present application, the preparation method of the arsenic-molybdenum hybrid polyacid salt comprises:

[0051] Ammonium molybdate is dissolved in water to obtain an ammonium molybdate aqueous solution;

[0052] The ammonium molybdate aqueous solution is stirred and As2O3, NaOH, CsCl, and 5-hydroxy-1,3-benzenedicarboxylic acid are added to obtain a mixed solution;

[0053] The mixed solution is heated under reflux at a temperature of 90-95°C (for example, 90°C, 91°C, 92°C, 93°C, 94°C, or 95°C), and then left to cool to room temperature;

[0054] The cooled mixed solution is filtered and left to volatilize, and a colorless and transparent arsenic-molybdenum hybrid polyacid salt crystal is obtained.

[0055] In some embodiments of the present application, when the arsenic-molybdenum hybrid polyacid salt is prepared, the mass ratio of water, ammonium molybdate, As2O3, NaOH, CsCl, and 5-hydroxy-1,3-benzenedicarboxylic acid is 15:0.53:0.05:0.06:0.10:0.14.

[0056] In some embodiments of the present application, the method for preparing potassium cobalt trioxalate comprises:

[0057] Oxalic acid and potassium oxalate are added to water and stirred to dissolve at 60°C, and then cobalt carbonate powder is added to obtain a first mixed solution;

[0058] The temperature of the first mixed solution is reduced to 35°C, and then lead dioxide and anhydrous acetic acid solution are added and stirred to obtain a second mixed solution;

[0059] The second mixed solution is subjected to standing cooling and suction filtration to obtain a filtrate;

[0060] Anhydrous ethanol is added to the filtrate to precipitate a crystalline substance;

[0061] The filtrate with the precipitated crystalline substance is filtered and dried to obtain potassium cobalt trioxalate.

[0062] In some embodiments of the present application, when preparing potassium cobalt trioxalate, the ratio of water, oxalic acid, potassium oxalate, cobalt carbonate, lead dioxide, anhydrous acetic acid, and anhydrous ethanol is 250 mL: 0.1 mol: 0.2 mol: 0.1 mol: 0.2 mol: 250 mL.

[0063] In some embodiments of the present application, when preparing potassium cobalt trioxalate, the drying temperature is 80°C.

[0064] In some embodiments of the present application, the method for preparing cobalt ammonium phosphate comprises:

[0065] A cobalt chloride hexahydrate aqueous solution is prepared according to a molar volume ratio of 0.5 mol / L;

[0066] Diammonium hydrogen phosphate is mixed with deionized water according to a molar volume ratio of 5 mol / L to obtain a supersaturated diammonium hydrogen phosphate solution;

[0067] The cobalt chloride hexahydrate aqueous solution and the supersaturated diammonium hydrogen phosphate solution are mixed and stirred at room temperature according to a volume ratio of 1:1, and after standing and aging, the supernatant is removed to obtain a lower layer turbid liquid;

[0068] The lower layer turbid liquid is washed with deionized water multiple times and filtered, and then dried to obtain cobalt ammonium phosphate.

[0069] In some embodiments of the present application, when preparing cobalt ammonium phosphate, the drying temperature is 85°C.

[0070] In order to better illustrate the present scheme, the following examples are provided.

[0071] Example

[0072] Step one: preparation of arsenic-molybdenum hybrid polyacid salt.

[0073] In 15 mL of water, 0.53 g of ammonium molybdate was dissolved while stirring, and 0.05 g of As203, 0.06 g of NaOH, 0.10 g of CsCl, and 0.14 g of 5-hydroxy-1,3-benzenedicarboxylic acid (H20IP) were slowly added to obtain a mixed solution. The mixed solution was heated at reflux at 93°C for 1 h, allowed to cool to room temperature, and then filtered, and allowed to stand to volatilize to obtain colorless transparent arsenic-molybdenum hybrid polyacid salt crystals.

[0074] Step two: preparation of potassium cobalt trioxalate.

[0075] In 250 mL of water, 0.1 mol of oxalic acid and 0.2 mol of potassium oxalate were dissolved while stirring at 60°C, and then 0.1 mol of cobalt carbonate powder was slowly added to obtain a first mixed solution. The temperature of the first mixed solution was reduced to 35°C, 0.1 mol of lead dioxide was slowly added, and then 0.2 mol of anhydrous acetic acid solution was added dropwise, and the stirring was continued for 1 h to obtain a second mixed solution. The second mixed solution was allowed to cool and stand, and then filtered to obtain a dark green filtrate. 250 mL of anhydrous ethanol was added to the filtrate to precipitate dark green crystalline material, which was filtered and dried at 80°C for 24 h to obtain potassium cobalt trioxalate.

[0076] Step three: preparation of ammonium cobalt phosphate.

[0077] In 200 mL of water, 0.1 mol of cobalt chloride hexahydrate was dissolved while stirring, and 1 mol of diammonium hydrogen phosphate was dissolved in 200 mL of deionized water while stirring for 3 min. The cobalt chloride hexahydrate solution was slowly poured into the supersaturated diammonium hydrogen phosphate solution, and stirred magnetically at room temperature for 1 h. The upper clear liquid was poured off after the solution was allowed to stand and age for 3 h, and the lower turbid liquid was washed with deionized water, filtered, and repeated 5 times. The product was dried at 85°C for 24 h to obtain ammonium cobalt phosphate.

[0078] Step four: preparation of a colorant.

[0079] The colorant was prepared by mixing 50% arsenic-molybdenum hybrid polyacid salt, 25% potassium cobalt trioxalate, and 25% ammonium cobalt phosphate by mass percentage.

[0080] Step five: preparation of concrete mix.

[0081] The cement and aggregate were mixed according to the proportions in Table 1, and water containing the colorant, water reducing agent, and air entraining agent was added during the mixing process to obtain a concrete mix.

[0082] Table 1: Proportions of mix ingredients (Kg / m 3 )

[0083]

[0084] Step six: pouring and demolding.

[0085] The concrete mixture is poured into the mold, vibrated and compacted, demolded after curing in a curing box for one day, and a demolded material is obtained.

[0086] Step seven: color matching.

[0087] The demolded material is heated from room temperature, with each temperature increase of 10 DEG C and holding for 5 min, and then the Lab color parameters of the demolded material are detected once by a color difference meter; after the redness a of the demolded material is close to the target redness, the temperature is kept unchanged, and the demolded material is irradiated by a xenon lamp, and the color of the demolded material is detected once every 5 min. During the heating process, the color of the repair material gradually changes from light green to light red brown, and then during the xenon lamp irradiation process, the color gradually changes to light brown yellow.

[0088] Finally, the NBS color difference DE of the color of the demolded material and the target color is calculated, and when the NBS color difference DE is less than 1.5, it is considered that the two colors are close, wherein the brightness L, the redness a, and the yellowness b of the color of the demolded material, and the brightness L0, the redness a0, and the yellowness b0 of the target color.

[0089] The color difference between the final color of the repair material and the target color is less than 1.5, which can effectively cover up the repair marks of the concrete of the water discharge structure and improve the aesthetic degree of the water discharge structure. In addition, the repair material of the present application can gradually change the color of the repair site by heating and xenon lamp irradiation, and does not need to find the amount of coloring material by multiple tests, which can greatly save the color matching time and material.

[0090] Finally, it should be noted that: the above only describes the preferred embodiments of the present application and is not used to limit the present application, although the present application has been described in detail with reference to the foregoing embodiments, and for those skilled in the art, the technical solutions recorded in the foregoing embodiments can be modified, or some technical features can be replaced, and any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.​

Claims

1. A repair material for a spillway structure, characterized by, The repair material comprises cement, aggregate, water and colorant; The cement, aggregate, water and colorant are mixed according to the engineering requirements; The colorant comprises arsenic-molybdenum hybrid polyacid salt, potassium cobalt trioxalate and cobalt ammonium phosphate; The preparation method of the arsenic-molybdenum hybrid polyacid salt comprises: Dissolving ammonium molybdate in water to obtain an ammonium molybdate aqueous solution; Stirring the ammonium molybdate aqueous solution and adding As2O3, NaOH, CsCl and 5-hydroxy-1,3-benzenedicarboxylic acid to obtain a mixed solution; Refluxing the mixed solution at a temperature of 90-95℃, and then standing and cooling to room temperature; Filtering the cooled mixed solution and standing and volatilizing to obtain colorless and transparent arsenic-molybdenum hybrid polyacid salt crystals; When preparing the arsenic-molybdenum hybrid polyacid salt, the mass ratio of water, ammonium molybdate, As2O3, NaOH, CsCl and 5-hydroxy-1,3-benzenedicarboxylic acid is 15:0.53:0.05:0.06:0.10:0.

14.

2. A repair material for a spillway according to claim 1, wherein The colorant comprises 50% arsenic-molybdenum hybrid polyacid salt, 25% potassium cobalt trioxalate and 25% cobalt ammonium phosphate by mass percentage.

3. A method for producing a repair material for a spillway structure, characterized by, The method comprises: Preparation of the colorant by using arsenic-molybdenum hybrid polyacid salt, potassium cobalt trioxalate and cobalt ammonium phosphate; Mixing cement and aggregate according to a preset ratio, and adding water in which the colorant is dissolved during the mixing process to obtain concrete mixture; Pouring the concrete mixture into a mold, vibrating and compacting, placing in a curing box for curing, and finally demolding to obtain demolding material; Adjusting the color of the demolding material by sequentially heating and irradiating the demolding material with a xenon lamp to obtain a repair material with a target color; The preparation method of the arsenic-molybdenum hybrid polyacid salt comprises: Dissolving ammonium molybdate in water to obtain an ammonium molybdate aqueous solution; Stirring the ammonium molybdate aqueous solution and adding As2O3, NaOH, CsCl and 5-hydroxy-1,3-benzenedicarboxylic acid to obtain a mixed solution; Refluxing the mixed solution at a temperature of 90-95℃, and then standing and cooling to room temperature; Filtering the cooled mixed solution and standing and volatilizing to obtain colorless and transparent arsenic-molybdenum hybrid polyacid salt crystals; When preparing the arsenic-molybdenum hybrid polyacid salt, the mass ratio of water, ammonium molybdate, As2O3, NaOH, CsCl and 5-hydroxy-1,3-benzenedicarboxylic acid is 15:0.53:0.05:0.06:0.10:0.

14.

4. A method of preparing a repair material for a spillway according to claim 3, wherein The preparation method of the potassium cobalt trioxalate comprises: Adding oxalic acid and potassium oxalate to water and stirring and dissolving at 60℃, and then adding cobalt carbonate powder to obtain a first mixed solution; Reducing the temperature of the first mixed solution to 35℃, and then adding lead dioxide and anhydrous acetic acid solution and stirring to obtain a second mixed solution; Standing and cooling the second mixed solution and suction filtering to obtain a filtrate; Adding anhydrous ethanol to the filtrate to precipitate crystals; Filtering and drying the filtrate with precipitated crystals to obtain potassium cobalt trioxalate.

5. A method of preparing a repair material for a spillway according to claim 4, wherein The ratio of water, oxalic acid, potassium oxalate, cobalt carbonate, lead dioxide, anhydrous acetic acid and anhydrous ethanol is 250 mL: 0.1 mol: 0.2 mol: 0.1 mol: 0.1 mol: 0.2 mol: 250 mL when the potassium cobalt trioxalate is prepared.

6. The method of claim 5, wherein the repair material of the spillway is prepared by mixing the cement with water in a ratio of 1:

1. The drying temperature is 80°C when the potassium cobalt trioxalate is prepared.

7. The method of claim 3, wherein the repair material is prepared by mixing the cement with water in a ratio of 1 : 1 to 1 :

2. The method for preparing the cobalt ammonium phosphate comprises the following steps: The cobalt chloride hexahydrate aqueous solution is prepared according to the molar volume ratio of 0.5 mol / L; The diammonium hydrogen phosphate is mixed with the deionized water according to the molar volume ratio of 5 mol / L to obtain a supersaturated diammonium hydrogen phosphate solution; The cobalt chloride hexahydrate aqueous solution and the supersaturated diammonium hydrogen phosphate solution are mixed at room temperature according to the volume ratio of 1:1, and the upper clear liquid is removed after standing and aging to obtain a lower turbid liquid; The lower turbid liquid is washed with deionized water for several times and filtered, and the cobalt ammonium phosphate is obtained after drying.

8. A method of preparing a repair material for a spillway according to claim 7, wherein The drying temperature is 85°C when the cobalt ammonium phosphate is prepared.

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