CN115572091A - Preparation method of steam-curing-free mineral admixture for pipe pile - Google Patents
Preparation method of steam-curing-free mineral admixture for pipe pile Download PDFInfo
- Publication number
- CN115572091A CN115572091A CN202211047342.XA CN202211047342A CN115572091A CN 115572091 A CN115572091 A CN 115572091A CN 202211047342 A CN202211047342 A CN 202211047342A CN 115572091 A CN115572091 A CN 115572091A
- Authority
- CN
- China
- Prior art keywords
- powder
- raw material
- mineral admixture
- grinding
- curing
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a preparation method of a non-steamed mineral admixture for pipe piles, which comprises the steps of preparing a powdery raw material, an active excitant and a grinding aid additive according to a certain mass ratio, feeding the powdery raw material, the active excitant and the grinding aid additive into a grinding device from a grinding head at a certain grinding speed, discharging the ground material at the tail of the grinding device to obtain a ground powdery material, preparing the ground powdery material and the workability improving additive according to a certain mass ratio, feeding the ground powdery material and the workability improving additive into a mixing device at a certain speed, and mixing to obtain the non-steamed mineral admixture for pipe piles. According to the invention, the powdery raw material with volcanic ash activity is secondarily processed into the ultrafine mineral admixture, so that the volcanic ash reaction activity of the powdery raw material is improved; further, under the action of an active exciting agent and a grinding aid additive, the volcanic ash reaction activity of the powder raw material is improved, the hydration reaction process of cementing materials such as cement is promoted, and further the steam-curing-free pipe pile concrete production process under the normal-temperature curing working condition is realized.
Description
Technical Field
The invention relates to a preparation method of an ultrafine mineral admixture, in particular to a preparation method of a steam-curing-free mineral admixture for a tubular pile, and belongs to the field of production and application of reinforced concrete tubular pile products.
Background
The reinforced concrete pipe pile is mainly used as a foundation structure of a building in actual engineering, and is widely applied to building engineering such as civil engineering, water conservancy, bridges, railways, port wharfs and the like. Jiang Yuanhai, liu Zhiyuan, liu Gongfei and the like, in research reports of analysis and treatment of low PHC pipe pile concrete autoclaving strength [ J ]. Concrete, 2013, (8): 120-122+126 ], the reinforced concrete pipe piles comprise prestressed concrete pipe piles (PC pipe piles), prestressed concrete thin-wall pipe piles (PTC pipe piles) and prestressed high-strength concrete pipe piles (PHC pipe piles), wherein the PHC pipe piles account for 80%.
The reinforced concrete pipe pile, especially the PHC pipe pile, has high requirements on the concrete strength and the production efficiency, and the 3d curing strength of the concrete reaches C80 and above. Peng Bo influence of steam curing system on high strength concrete performance [ D ]. Wuhan Hubei: research in Wuhan university of science and technology, 2007, finds that the hydration process of cement and other cementing materials in concrete can be remarkably accelerated by adopting a high-temperature curing system, the early strength of concrete is promoted to be improved, and the influence on hydration products of cement and other cementing materials is small. A further research result of Li Meng round application research of mineral admixtures with large mixing amount in steam-cured concrete [ D ]. Beijing, qinghua university, 2015 ] shows that hydration products in steam-cured concrete have large crystal sizes and few connecting points, have a good promotion effect on the early strength development of the concrete, and have certain adverse effects on the later strength increase and durability of the concrete. Zhang Jiangang and so on, the hydration characteristics and the microstructure of mineral admixtures under steam curing conditions [ J ]. The electron microscopy report, 2015,34 (2): 106-110, researches show that in steam-cured concrete, the mineral admixtures such as ground quartz sand, silica fume, fly ash, mineral powder and so on are used for replacing 20-30% of cement as a cementing material, so that the working performance, the mechanical property and the durability of the steam-cured concrete can be obviously improved.
With the new development trend of the PHC tubular pile concrete industry, the steam curing time and the steam curing temperature of the PHC tubular pile concrete are reduced or the steam curing is not required, and the method has important significance for promoting cost reduction, efficiency improvement, energy conservation and emission reduction of the whole tubular pile concrete industry.
5363 research and development and production application of steam curing-free and steam pressure-free prestressed concrete pipe piles such as Feng Naiqian [ C ]// CCPA precast concrete pile party and China silicate society reinforced concrete product professional committee 2013-2014 annual meeting academic exchange text collection 2014 ] research shows that depending on high-temperature climatic conditions in Hainan, concrete is prepared by using micro-bead powder and superfine mineral powder, curing is carried out in a self-made solar curing shed, the temperature of the curing shed is about 40-60 ℃, and steam curing is replaced by solar curing, so that the concrete obtains high early strength. However, the solar energy is used for maintenance, which is influenced by weather, especially rainy weather in the south, and thus, a lot of problems are caused in practical production application.
Tae-from.Min et al, experimental stub on the level of compressive string of early concrete using calcium-based concrete and high early string of cement J, structural, building, 2014,64 (3), 208-214, indicate that calcium formate is added as an early strength agent on the basis of early strength cement, and the prepared concrete is cured at room temperature for 6 hours, the compressive strength reaches more than 10MPa, and the requirements on the demolding strength of corresponding prefabricated concrete members are met, but the demolding strength is far away from the pipe pile.
Zhao Shiyu research on steam-free curing of PHC tubular pile concrete [ D ]. Jiangsu Nanjing: research and development of the southeast university, 2017, discovers that the die sinking spool pile concrete with the slump of 30-70mm is prepared by using a polycarboxylic acid early strength water reducing agent, triethanolamine or anhydrous sodium sulfate as an early strength agent, an ultrafine mineral admixture and the like as technical means, and a normal-temperature curing mode is adopted, so that the concrete meets the technical requirements that the demolding strength reaches 45MPa within 18 hours, the 3d strength reaches 80MPa, and the actually measured strength of a drill core reaches more than 90 MPa.
In conclusion, the admixture, the early strength agent, the ultrafine mineral admixture and the like are adopted as technical means, so that certain progress is made in the aspect of research on the steam-curing-free tubular pile concrete, but obvious differences exist in the aspects of key technical requirements of tubular pile production such as the requirements of normal-temperature curing temperature, normal-temperature curing time, production cost, demolding strength and the like.
Based on the above, there is a need to develop a preparation method of a mineral admixture for steam-curing-free pipe pile concrete, which is simple in preparation, good in workability, high in economy and high in curing strength.
Disclosure of Invention
The invention aims to provide a preparation method of a mineral admixture for steam curing-free pipe pile concrete, which is simple to prepare, good in workability, high in economy and high in curing strength, and particularly relates to a normal-temperature synthesis method of a polycarboxylic acid water reducing agent taking a polyether macromonomer as a raw material.
The invention realizes the aim through the following technical scheme, and the preparation method of the steam-curing-free mineral admixture for the pipe pile comprises the following steps,
s1, preparing a powder raw material, an active exciting agent and a grinding aid additive according to a certain mass ratio, feeding the powder raw material, the active exciting agent and the grinding aid additive into a grinding device from a grinding head at a certain grinding speed, wherein the grinding speed is the same as the grinding speed, and discharging from the tail of a mill to obtain a ground powder material;
the powder raw material is a powder raw material with volcanic ash activity, and specifically comprises cement clinker powder, raw ash, coarse ash, secondary ash, S75 mineral powder, S95 mineral powder, silica fume, lithium slag powder, volcanic ash and zeolite powder, wherein the cement clinker powder, the S75 mineral powder and the S95 mineral powder are necessary raw materials, the three raw materials are in any mass ratio, and the mass ratio of the three raw materials in the powder raw material is 40-70%; the mass ratio of the silica fume in the powder raw material is less than or equal to 10 percent; the mass ratio of the residual powder raw materials is prepared in any mass ratio;
the dosage of the active excitant is 5 to 10 percent of the total mass of the powder raw materials;
the grinding aid additive comprises a liquid material A, a liquid material B and a solid material C, wherein the liquid material A is a nano calcium silicate suspension, the liquid material B is esterified amine polyether polyol, and the solid material C comprises one or more of anhydrous sodium sulphate, sodium nitrite, calcium nitrite, tetrahydrate calcium nitrate, sodium thiocyanate, ammonium thiocyanate, calcium thiocyanate, sodium sulfite and sodium thiosulfate;
the dosage of the liquid A material is 0.1-0.5% of the total mass of the powder raw material, the dosage of the liquid B material is 0.02-0.05% of the total mass of the powder raw material, and the dosage of the solid C material is 0.1-0.5% of the total mass of the powder raw material;
s2, preparing the ground powder material prepared in the step S1 and the workability improving additive according to a certain mass ratio, feeding the mixture into a mixing device at a certain speed, and mixing to obtain a mineral admixture for the non-steamed pipe pile;
the dosage of the workability improving additive is 10-30% of the mass of the milled powder material.
Preferably, the activity activator comprises one or more of limestone powder, calcium hydroxide powder, natural gypsum powder, desulfurized gypsum powder, phosphogypsum powder and alunite powder.
Preferably, the suspension of nano calcium silicate is a commercial product, the commercial product contains 10-20% of solid calcium silicate, the pH value is above 12, and the nano particle size of calcium silicate particles is 100-300 nm.
Preferably, the molecular structural formula of the acid esterified amine-based polyether polyol is as follows,
wherein R1, R2 and R3 are one of H and-CH 3, and n is a positive integer between 0 and 7.
Preferably, the specific surface area of the milled powder material obtained in step S1 is 700-1000 m 2 Per Kg; the fineness is less than or equal to 3 percent; median particle diameter (D) 50 ) Is 3-7 μm.
Preferably, the specific surface area of the mineral admixture for the steam-curing-free pipe pile obtained in the step S2 is 550-750 m 2 Per Kg; the fineness is less than or equal to 5 percent; median particle diameter (D) 50 ) 5-10 μm, the steam curing activity is more than or equal to 110 percent.
Preferably, the workability improving additive of step S2 comprises air classification of first grade ash and microbeads.
The invention has the beneficial effects that: the invention discloses a normal-temperature synthesis method of a polycarboxylic acid water reducing agent by taking a polyether macromonomer as a raw material, which has obvious advantages in the following aspects:
1. according to the invention, the powdery raw material with volcanic ash activity is secondarily processed into the ultrafine mineral admixture, so that the volcanic ash reaction activity of the powdery raw material is improved; further, under the action of an active exciting agent and a grinding aid additive, the volcanic ash reaction activity of powder raw materials is improved, the hydration reaction process of cementing materials such as cement is promoted, and further the steam-curing-free pipe pile concrete production process under the normal-temperature curing working condition is realized.
2. The activity excitant disclosed by the invention fully exerts the hydration activity of alkali excitation and sulfate excitation effects on powder raw materials with pozzolana reaction activity such as fly ash and mineral powder, reduces the dosage of cement clinker in concrete, and has the obvious effects of saving cement production energy consumption and carbon dioxide emission.
3. The grinding aid additive comprises three components: the liquid A material and the nano calcium silicate suspension provide nano calcium silicate particles as seed crystals, so that the hydration process of cement and other cementing materials is promoted, and the early strength effect is remarkable. Furthermore, the strong alkalinity of the nano calcium silicate suspension liquid has an alkali excitation effect on the mineral admixture, and promotes the hydration reaction of the mineral admixture; the liquid B material and the esterified amino polyether polyol have good grinding-assisting effect and normal-temperature concrete curing activity improving effect, are beneficial to improving the grinding processing efficiency of powder raw materials, reducing the grinding processing energy consumption or improving the technical indexes such as the specific surface area of the ground powder materials; the solid C material is inorganic salt with early strength effect and no halogen ion, promotes the hydration process of cementing materials such as cement and the like, and improves the early strength of concrete. The three components of the grinding aid additive act synergistically to endow the powder raw material with high-efficiency processing efficiency and good normal-temperature maintenance activity and strength.
4. According to the mineral admixture, the workability improving additive is introduced to optimize technical indexes such as particle distribution of the mineral admixture, the ball effect and the water saving effect of the additive are fully exerted, the influence of the mineral admixture with low fineness and large specific surface area on concrete workability under the working condition of low water-cement ratio is improved, and the low water-cement ratio and the construction performance of pipe pile concrete are guaranteed.
5. The invention designs the grinding device, fully considers the requirement of the grinding device on the particle size of the powder raw material, optimizes the bin dividing structure, the ball forging type, the grading and the loading capacity in the grinding device to be matched with the particle size change of the material in the grinding process, fully exerts the grinding effect of the grading ball forging, and ensures the grinding efficiency of the material in the grinding device.
Drawings
FIG. 1 is a process flow chart of the invention for producing mineral admixture for non-steam-curing pipe pile.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The powder raw materials in the invention are all commercial products, the parts are specified in the examples as mass parts, and the addition amount of other materials is converted into mass parts.
The specific surface area is measured by using a DBT127 type Boehringer gas permeability specific surface area meter;
in the invention, the fineness uses an FSY-150B cement fineness negative pressure screen analyzer to measure the screen allowance of a 30-micron square-hole screen, and the screen allowance accounts for the total material amount by mass percent to obtain the fineness;
median particle diameter (D) in the invention 50 ) And particle size distribution were measured using a BT9300 type laser particle size analyzer.
The steam-curing activity of the mortar in the invention is tested by referring to a method specified in JC/T2554-2019 admixture for steam-curing concrete products.
A preparation method of a mineral admixture for a tubular pile without steam curing comprises the following steps,
s1 preparation of milled powder material
The method comprises the following steps of preparing a powder raw material, an active exciting agent and a grinding aid additive according to a certain mass ratio, feeding the powder raw material, the active exciting agent and the grinding aid additive into a grinding device from a grinding head at a certain grinding speed, discharging the powder raw material from the tail of a mill at the same grinding speed as the grinding speed, and obtaining a ground powder material.
The powder raw material is a powder raw material with volcanic ash activity, and specifically comprises cement clinker powder, raw ash, coarse ash, secondary ash, S75 mineral powder, S95 mineral powder, silica fume, lithium slag powder, volcanic ash and zeolite powder, wherein the cement clinker powder, the S75 mineral powder and the S95 mineral powder are necessary raw materials, the three raw materials are in any mass ratio, and the mass ratio of the three raw materials in the powder raw material is 40-70%; the mass ratio of the silica fume in the powder raw material is less than or equal to 10 percent; the mass ratio of the rest powder raw materials is prepared in any mass ratio.
The dosage of the active excitant is 5-10% of the total mass of the powder raw materials, and the active excitant comprises one or more of limestone powder, calcium hydroxide powder, natural gypsum powder, desulfurized gypsum powder, phosphogypsum powder and alunite powder.
The grinding aid additive is divided into a liquid material A, a liquid material B and a solid material C, wherein the liquid material A is nano calcium silicate suspension, also called hydrated C-S-H gel, a polycarboxylate water reducing agent is generally used as a dispersing agent, a sodium silicate aqueous solution and a calcium salt aqueous solution are simultaneously dripped into the polycarboxylate water reducing agent aqueous solution to react to generate nano calcium silicate, and the nano calcium silicate is suspended in the aqueous solution, the preparation method is well known by practitioners in the industry, so that no repeated description is needed in the invention, the commercially available hydrated nano calcium silicate is directly purchased for use, the solid content of the commercially available product is 10-20%, the pH value is above 12, the nano particle size of calcium silicate particles is 100-300 nm, and the main technical indexes of the commercially available nano calcium silicate suspension are shown in Table 1.
TABLE 1 Main technical indices of commercially available nano calcium silicate suspensions
The liquid B material is esterified amine polyether polyol, mainly carboxylic acid esterified polyether polyol or phosphonic acid esterified polyether polyol. The amido polyether polyol takes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine, polyethylene imine and the like as initiators, and ethylene oxide and propylene oxide are epoxy monomers, and the ratio of the ethylene oxide to the propylene oxide is 1: (1.0-1.1) n, wherein n is the number of hydroxyl hydrogen or amino hydrogen contained in the initiator. The esterified polyether polyol is prepared by reacting polyether polyol with an esterification reagent. The esterification reagent comprises carboxylic acid esterification reagents such as maleic anhydride, phosphorus pentoxide and polyphosphoric acid or phosphonic acid esterification reagents, and the polyether polyol and the esterification reagents are mixed according to the proportion of 1: (1.0-1.1) in a molar ratio. The preparation method is well known to those skilled in the art, and therefore, the detailed description is omitted in the present invention, and the commercially available phosphonated amino polyether polyol is directly purchased for use in the present invention.
The molecular structural formula of the acid esterified amino polyether polyol is as follows,
wherein R1, R2 and R3 are one of H and-CH 3, and n is a positive integer between 0 and 7.
The commercially available phosphonated amino polyether polyol and the code are shown in table 2.
TABLE 2 commercially available phosphonated amino polyether polyols and designations
The solid C material comprises one or more of anhydrous sodium sulphate, sodium nitrite, calcium nitrite, tetrahydrate calcium nitrate, sodium thiocyanate, ammonium thiocyanate, calcium thiocyanate, sodium sulfite and sodium thiosulfate.
The dosage of the liquid A material is 0.1-0.5% of the total mass of the powder raw material, the dosage of the liquid B material is 0.02-0.05% of the total mass of the powder raw material, and the dosage of the solid C material is 0.1-0.5% of the total mass of the powder raw material.
Before the preparation of the milled powder material, the granular or blocky raw materials in the powder raw materials are pre-crushed, and the particle size of the granules is reduced to be less than 2mm so as to meet the processing requirement of milling.
The grinding device is a commercially available vertical grinding machine, and comprises a pre-grinding device connected to the grinding device, and the component structure and the working principle of the pre-grinding device are well known by practitioners in the industry, so that the detailed description is omitted in the invention.
The tube mill in the grinding device comprises an open-path tube mill and a closed-path tube mill, the specification sizes of the tube mills are 3.2m multiplied by 11m,3.2m multiplied by 13m,3.2m multiplied by 15m,3.5m multiplied by 13m,3.5m multiplied by 15m,3.5m multiplied by 17m, 3.8m multiplied by 13m,3.8m multiplied by 15m,3.8m multiplied by 17m,4.2m multiplied by 13m,4.2m multiplied by 15m,4.2m multiplied by 17m, etc., the tube mills are filled with steel balls or steel forgings as grinding fittings, are sold steel balls or steel forgings, are generally steel alloy materials containing nickel and chromium, the loading amount of the steel balls or steel forgings is 15% -30% of the volume in the tube mill, the diameter of the steel balls is 40mm,30mm, 10mm,8mm,6mm,5mm, etc.; the steel forging is 40 mm. Times.40mm, 30mm. Times.30mm, 20mm. Times.20mm, 15mm. Times.15mm, 10mm. Times.10 mm,8 mm. Times.8mm, 6mm. Times.6mm, 5mm. Times.5 mm, and the like.
The ball forging gradation of each bin section in the tube mill is as follows: the grain diameter of the steel ball or steel forging grains in the first bin section is 15-40 mm, and each grain diameter accounts for one fourth; the grain diameter of the steel ball or steel forging grains in the second bin section is 8-20 mm, and each grain diameter accounts for one fourth; the grain diameter of the grains in the third bin section is 6-15 mm, and each grain diameter accounts for one fourth; the particle size of the particles in the fourth bin section is 5-10 mm, and each particle size accounts for one fourth.
The invention directly purchases HLMX superfine vertical type pulverizer of Guilin Hongcheng mine equipment manufacturing Limited liability company, and the tube mill size of the pulverizing device, the steel ball/steel forging gradation of each bin section in the mill and the dosage ratio are shown in Table 3.
Table 3 size of the grinding device, steel ball/steel forging gradation of each bin section in the mill and the amount used in the embodiment
Preparation of mineral admixture for S2 non-steamed tubular pile
Preparing the ground powder material prepared in the step S1 and the workability improving additive according to a certain mass ratio, feeding the mixture into a mixing device at a certain speed, and mixing to obtain a mineral admixture for the non-steamed tubular pile;
the dosage of the workability improving additive is 10-30% of the mass of the milled powder material.
The workability improving additive comprises air separation first-grade ash and micro-beads, fully exerts the ball effect and the water-saving effect of the additive, solves the problem of concrete workability caused by high material viscosity of a mineral admixture under the working condition of low water-cement ratio, and distributes Fang Bianguan pile concrete in a die sinking line or pumping line process.
The specific surface area of the milled powder material obtained in the step S1 is 700-1000 m 2 Per Kg; the fineness is less than or equal to 3 percent; median particle diameter (D) 50 ) Is 3-7 μm.
The specific surface area of the mineral admixture for the steam-curing-free pipe pile obtained in the step S2 is 550-750 m 2 Per Kg; the fineness is less than or equal to 5 percent; median particle diameter (D) 50 ) 5-10 μm, the steam curing activity is more than or equal to 110 percent.
The preparation process flow of the mineral admixture for the non-steamed pipe pile disclosed by the invention is shown in figure 1.
After a powder raw material, an active exciting agent and a grinding aid additive are prepared according to a certain mass ratio, the powder raw material, the active exciting agent and the grinding aid additive are metered and conveyed to a grinding head of a grinding device through different pipelines or belt conveying devices; wherein, the blocky raw material is processed into powder with the particle size less than 2mm through a pre-grinding device so as to meet the processing requirement of a tube mill entering a grinding mill, and then the powder is conveyed to a grinding head of the grinding device. The materials continuously enter the grinding device at a grinding head of the grinding device at a certain speed.
In this embodiment, the grinding head feeding rate of the grinding device is the same as the tail discharging rate, and the feeding rate of the raw material is generally adjusted by the tail discharging rate. The powder discharging rate of the mill tail is generally called as the powder discharging amount of the mill tail of the grinding device in 1 hour of production bench. After being ground and processed by the grinding device, the ground powder is discharged from the grinding tail of the grinding device to obtain ground powder materials.
Example 1
Grinding processing steps: the feeding speed of the raw materials of the cement clinker, S75 mineral powder, raw ash, lithium slag powder and other powder is 30.0t/h, and the raw materials are prepared according to the mass ratio of 15.0 percent to 30.0 percent to 60.0 percent to 5.0 percent, wherein the cement clinker is in a block shape and needs to be treated by a pre-grinding device. The active excitant is limestone powder and natural gypsum powder, and the dosage of the limestone powder and the natural gypsum powder is respectively 2.0 percent and 3.0 percent of the mass of the powder raw material. The liquid material A in the grinding aid additive is CSH-I, and the using amount of the liquid material A is 0.1 percent of the mass of the powder raw material; the liquid B material is ZM-1, and the using amount of the liquid B material is 0.02 percent of the mass of the powder raw material; the solid material C is anhydrous sodium sulphate, and the dosage of the solid material C is 0.3 percent of the mass of the powder raw material. The materials are fed at a grinding head of the grinding device, the grinding speed or the grinding time of the materials out of a grinding table is 31.6t/h, and tests show that the fineness of the ground powder materials is 3.0 percent and the specific surface area is 800m 2 Kg, median particle diameter (D) 50 ) It was 6.0. Mu.m.
The workability improving additive is microbeads, the feeding rate is 3.2t/h, the feeding rate of the ground powder material is 31.6t/h, the two materials simultaneously enter a spiral reamer conveyor to be mixed to obtain a mineral admixture for the non-steamed tubular pile, the mineral admixture is named as CHL-1, and the fineness of the ground powder material is 3.5 percent and the specific surface area is 700m through tests 2 Kg, median particle diameter (D) 50 ) It was 7.0. Mu.m.
Example 2
Grinding processing steps: feeding speed of powdery raw materials such as cement clinker, S95 mineral powder, coarse ash, silica fume and the likeIs 35.0t/h, and is prepared according to the mass ratio of 10.0 percent to 50.0 percent to 45.0 percent to 5.0 percent, wherein the cement clinker is in a block shape and needs to be treated by a pre-grinding device. The active excitant is calcium hydroxide powder, and the dosage of the calcium hydroxide powder is respectively 8.0 percent of the mass of the powder raw material. The liquid material A in the grinding aid additive is CSH-II, and the using amount of the liquid material A is 0.3 percent of the mass of the powder raw material; the liquid B material is ZM-2, and the using amount of the liquid B material is 0.05 percent of the mass of the powder raw material; the solid C material is calcium nitrite, and the using amount of the solid C material is 0.5 percent of the mass of the powder raw material. The materials are fed at a grinding head of the grinding device, the grinding speed or the grinding time of the materials out of a grinding table is 38.1t/h, and tests show that the fineness of the ground powder materials is 1.9 percent and the specific surface area is 900m 2 Kg, median particle diameter (D) 50 ) And was 4.0 μm.
The workability improving additive is winnowing first-grade ash with the feeding rate of 7.62t/h and the feeding rate of ground powder material of 38.1t/h, the two materials simultaneously enter a spiral reamer conveyor for material mixing to obtain a mineral admixture for the non-steamed tubular pile, which is named as CHL-2, and tests show that the fineness of the ground powder material is 5.0 percent and the specific surface area is 650m 2 Kg, median particle diameter (D) 50 ) It was 8.0. Mu.m.
Example 3
Grinding processing steps: s95 powdered raw materials such as mineral powder, secondary ash, silica fume and the like are fed at a rate of 40.0t/h and are prepared according to a mass ratio of 50.0% to 40.0% to 10.0%. The active excitant is desulfurized gypsum powder, and the dosage of the desulfurized gypsum powder is respectively 10.0 percent of the mass of the raw materials of the powder. The liquid material A in the grinding aid additive is CSH-III, and the using amount of the liquid material A is 0.5 percent of the mass of the powder raw material; the liquid B material is ZM-3, and the using amount of the liquid B material is 0.02 percent of the mass of the powder raw material; the solid C material is sodium thiocyanate, and the dosage of the solid C material is 0.4 percent of the mass of the powder raw material. The materials are fed at a grinding head of the grinding device, the grinding speed or the grinding table discharging time is 44.4t/h, and tests show that the fineness of the ground powder material is 0.8 percent and the specific surface area is 1000m 2 Kg, median particle diameter (D) 50 ) And 3.0 μm.
The workability-improving additive was microbeads at a feed rate of 13.3t/h. The feeding rate of the ground powder material is 44.4t/h, and the two materials simultaneously enter the spiral reamer for conveyingMixing the materials by a machine to obtain a mineral admixture for the non-steamed tubular pile, which is named as CHL-3, and testing shows that the fineness of the ground powder material is 6.0 percent and the specific surface area is 610m 2 Kg, median particle diameter (D) 50 ) And 9.0 μm.
Example 4
Grinding processing steps: s75, feeding rate of powdered raw materials such as mineral powder, secondary ash, zeolite powder and the like is 45.0t/h, and the powdered raw materials are prepared according to the mass ratio of 45.0% to 40.0% to 15.0%. The active excitant is natural gypsum powder, and the dosage of the natural gypsum powder is respectively 6.0 percent of the mass of the raw materials of the powder. The liquid material A in the grinding aid additive is CSH-I, and the using amount of the liquid material A is 0.4 percent of the mass of the powder raw material; the liquid B material is ZM-4, and the using amount of the liquid B material is 0.04 percent of the mass of the powder raw material; the solid C material is ammonium thiocyanate, and the dosage of the solid C material is 0.3 percent of the mass of the powder raw material. The materials are fed at a grinding head of the grinding device, the grinding speed or the grinding time of the materials out of a grinding table is 48.0t/h, and tests show that the fineness of the ground powder materials is 2.3 percent, and the specific surface area is 800m 2 Kg, median particle diameter (D) 50 ) It was 4.8 μm.
The workability improving additive is air separation first-grade ash, and the feeding rate is 14.4t/h. The feeding speed of the ground powder material is 48.0t/h, the two materials simultaneously enter a spiral reamer conveyor for material mixing to obtain a mineral admixture for the steam-curing-free pipe pile, which is named as CHL-4, and tests show that the ground powder material has the fineness of 7.0 percent and the specific surface area of 570m 2 Kg, median particle diameter (D) 50 ) Is 10.0. Mu.m.
Example 5
Grinding processing steps: the feeding speed of the raw powder materials such as cement clinker, S75 mineral powder, secondary ash, lithium slag powder and the like is 35.0t/h, and the raw powder materials are prepared according to the mass ratio of 15.0 to 30.0 to 40.0 to 15 percent, wherein the cement clinker is blocky and needs to be treated by a pre-grinding device. The active excitant is phosphogypsum powder, and the dosage of the phosphogypsum powder is 6.0 percent of the mass of the raw material of the powder respectively. The liquid material A in the grinding aid additive is CSH-I, and the using amount of the liquid material A is 0.2 percent of the mass of the powder raw material; the liquid B material is ZM-5, and the using amount of the liquid B material is 0.03 percent of the mass of the powder raw material; the solid C material is calcium thiocyanate, and the dosage of the solid C material is 0.5 percent of the mass of the powder raw material. The above materials are inThe grinding head of the grinding device is used for feeding, the grinding speed or the grinding time of the grinding head is 37.4t/h, and tests show that the fineness of the ground powder material is 1.8 percent and the specific surface area is 850m 2 Kg, median particle diameter (D) 50 ) And 4.5 μm.
The workability improving additive is air separation first-grade ash, and the feeding rate is 5.6t/h. The feeding rate of the ground powder material is 37.4t/h, the two materials simultaneously enter a spiral reamer conveyor for material mixing to obtain a mineral admixture for the steam-curing-free pipe pile, which is named as CHL-5, and tests show that the ground powder material has the fineness of 3.8 percent and the specific surface area of 680m 2 Kg, median particle diameter (D) 50 ) It was 7.5 μm.
Example 6
Grinding processing steps: the feeding speed of the raw powder materials such as cement clinker, S95 mineral powder, coarse ash, lithium slag powder and the like is 50.0t/h, and the raw powder materials are prepared according to the mass ratio of 10.0 to 40.0 to 10 percent, wherein the cement clinker is blocky and needs to be treated by a pre-grinding device. The active excitant is calcium hydroxide powder and desulfurized gypsum powder; the dosage of the calcium hydroxide powder and the desulfurization gypsum powder is respectively 6.0 percent and 4 percent of the mass of the raw material of the powder. The liquid material A in the grinding aid additive is CSH-III, and the using amount of the liquid material A is 0.4 percent of the mass of the powder raw material; the liquid B material is ZM-6, and the using amount of the liquid B material is 0.04 percent of the mass of the powder raw material; the solid material C is sodium thiosulfate, and the dosage of the solid material C is 0.4 percent of the mass of the powder raw material. The materials are fed at a grinding head of the grinding device, the grinding speed or the grinding table discharging time is 55.4t/h, and tests show that the fineness of the ground powder material is 3.0 percent and the specific surface area is 700m 2 Kg, median particle diameter (D) 50 ) It was 6.8 μm.
The workability improving additive was microbeads and the feed rate was 11.1t/h. The feeding speed of the ground powder material is 55.4t/h, the two materials simultaneously enter a spiral reamer conveyor for material mixing to obtain a mineral admixture for the steam-curing-free pipe pile, which is named as CHL-6, and the test shows that the ground powder material has the fineness of 5.8 percent and the specific surface area of 580m 2 Kg, median particle diameter (D) 50 ) It was 8.5 μm.
Comparative example 1
Grinding: cement clinker, S95 mineral powder,The feeding speed of the raw materials of the powder such as coarse ash, zeolite powder and the like is 40.0t/h, the raw materials are prepared according to the mass ratio of 10.0 percent to 75.0 percent to 5 percent, wherein the cement clinker is in a block shape and needs to be treated by a pre-grinding device. The activity excitant is natural gypsum powder; the dosage of the natural gypsum powder is 5.0 percent of the mass of the powder raw material. The material A in the grinding aid additive is CSH-II, and the using amount of the material A is 0.5 percent of the mass of the powder raw material; the liquid B material is ZM-2, and the using amount of the liquid B material is 0.05 percent of the mass of the powder raw material; the solid material C is calcium nitrate tetrahydrate, and the using amount of the solid material C is 1.0 percent of the mass of the powder raw material. The materials are fed at a grinding head of the grinding device, the grinding speed or the grinding table is 42.4t/h, and the mineral admixture for the steam-curing-free pipe pile is obtained and named as CHL-7. The test shows that the fineness of the ground powder material is 1.0, and the specific surface area is 950m 2 Kg, median particle diameter (D) 50 ) And was 4.0 μm.
Comparative example 2
The workability improving additive was microbeads and the feed rate was 12.0t/h. S105, feeding the mineral powder at a speed of 28.0t/h, simultaneously feeding the two materials into a spiral reamer conveyor for material mixing to obtain a mineral admixture named CHL-8, and testing that the fineness of the ground powder material is 8.9 percent and the specific surface area is 550m 2 Kg, median particle diameter (D) 50 ) And 10.5 μm.
Application example 1
The performance of the mineral admixture for the non-steamed pipe pile is tested by using a mortar test. The extension degree of the mortar is tested according to the regulations in GB/T8077-2012 (test method for homogeneity of concrete admixture), and the molding mortar test block in the standard T0506-2005 (method for detecting strength of cement mortar) is referred. The mixture ratio of the raw materials of the mortar test is that the sea snail 525 cement 315g, the mineral admixture 135g, the standard sand 1350g, the water reducing agent deflection mixing amount 0.14%, the mixing water 135g, and the mortar test data is shown in table 4.
TABLE 4 mortar test for admixtures
As can be seen from the data in Table 4, the mineral admixture for the non-steamed pipe pile of the present invention has better vibration expansion degree in the mortar test, and the height is 15-20mm compared with pure cement. Compared with pure cement, the 1d standard curing strength and the 3d standard curing strength of the mortar have better effect of improving the strength of the mortar test block. In addition, the application effect of the mineral admixture for the non-steamed pipe pile is better than that of the mineral admixture in the comparative example.
Application example 2
The performance of the admixtures was tested using the concrete test. The concrete slump is tested according to the regulations in GB/T8076-2008 'concrete admixture', and the concrete test block is formed according to the regulations in GB/T50081-2002 'Standard test method for mechanical Properties of ordinary concrete'. The adopted cement is conch 525 cement, the sand is medium sand with fineness modulus Mx =2.6, the mineral admixture replaces 30% of cement to be used as a cementing material, and the pebbles are continuous graded broken stones with the grain size of 5-20mm. The concrete test raw material formulation is shown in table 5.
TABLE 5 concrete raw material proportioning table
The mineral admixtures prepared in the respective examples were subjected to concrete test and the results are shown in Table 6.
TABLE 6 concrete test testing of mineral admixtures
As can be seen from the data in Table 6, the use of the mineral admixture for the steam-curing-free pipe pile of the invention can improve the slump of concrete by 20-30mm, and the workability of the concrete is good. By using the mineral admixture for the steam curing-free pipe pile, the 1d standard curing strength and the 3d standard curing strength of concrete are greatly improved compared with pure cement, the 1d standard curing strength of concrete is not lower than 45MPa, and the strength requirements of dismantling and transferring a mould of pipe pile concrete to a storage yard are met. Furthermore, the standard curing strength of the 3d concrete reaches more than 70MPa, and the production requirement of the tubular pile concrete with the strength grades of C60 and C70 is completely met. In addition, the concrete slump and the compressive strength of the mineral admixture for the steam-curing-free pipe pile are better than those of the mineral admixture in the comparative example.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.
Claims (7)
1. A preparation method of a steam-curing-free mineral admixture for a tubular pile is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, preparing a powder raw material, an active exciting agent and a grinding aid additive according to a certain mass ratio, feeding the powder raw material, the active exciting agent and the grinding aid additive into a grinding device from a grinding head at a certain grinding speed, discharging the powder raw material from the tail of a mill at the same grinding speed as the grinding speed, and obtaining a ground powder material;
the powder raw material is a powder raw material with volcanic ash activity, and specifically comprises cement clinker powder, raw ash, coarse ash, secondary ash, S75 mineral powder, S95 mineral powder, silica fume, lithium slag powder, volcanic ash and zeolite powder, wherein the cement clinker powder, the S75 mineral powder and the S95 mineral powder are necessary raw materials, the three raw materials are in any mass ratio, and the mass ratio of the three raw materials in the powder raw material is 40-70%; the mass ratio of the silica fume in the powder raw material is less than or equal to 10 percent; the mass ratio of the residual powder raw materials is prepared in any mass ratio;
the dosage of the active excitant is 5 to 10 percent of the total mass of the powder raw materials;
the grinding aid additive comprises a liquid material A, a liquid material B and a solid material C, wherein the liquid material A is a nano calcium silicate suspension, the liquid material B is esterified amine polyether polyol, and the solid material C comprises one or more of anhydrous sodium sulphate, sodium nitrite, calcium nitrite, tetrahydrate calcium nitrate, sodium thiocyanate, ammonium thiocyanate, calcium thiocyanate, sodium sulfite and sodium thiosulfate;
the dosage of the liquid A material is 0.1-0.5% of the total mass of the powder raw material, the dosage of the liquid B material is 0.02-0.05% of the total mass of the powder raw material, and the dosage of the solid C material is 0.1-0.5% of the total mass of the powder raw material;
s2, preparing the milled powder material prepared in the step S1 and a workability improving additive according to a certain mass ratio, feeding the materials into a mixing device at a certain speed, and mixing to obtain a mineral admixture for the non-steamed pipe pile;
the dosage of the workability improving additive is 10-30% of the mass of the milled powder material.
2. The preparation method of the mineral admixture for the steam-curing-free pipe pile as claimed in claim 1, wherein the mineral admixture comprises the following steps: the active excitant comprises one or more of limestone powder, calcium hydroxide powder, natural gypsum powder, desulfurized gypsum powder, phosphogypsum powder and alunite powder.
3. The preparation method of the mineral admixture for the steam-curing-free pipe pile as claimed in claim 1, wherein the mineral admixture comprises the following steps: the suspension of the nano calcium silicate is a commercial product, the solid content of the commercial product is 10-20%, the pH value is above 12, and the nano particle size of calcium silicate particles is 100-300 nm.
4. The preparation method of the mineral admixture for the steam-curing-free pipe pile as claimed in claim 1, wherein the mineral admixture comprises the following steps: the molecular structural formula of the acid esterified amino polyether polyol is as follows,
wherein R1, R2 and R3 are one of H and-CH 3, and n is a positive integer between 0 and 7.
5. The preparation method of the mineral admixture for the steam-curing-free pipe pile according to claim 1, characterized by comprising the following steps: the specific surface area of the milled powder obtained in the step S1 is 700-1000 m 2 Per Kg; the fineness is less than or equal to 3 percent; median particle diameter (D) 50 ) Is 3-7 μm.
6. The preparation method of the mineral admixture for the steam-curing-free pipe pile as claimed in claim 1, wherein the mineral admixture comprises the following steps: the specific surface area of the mineral admixture for the steam-curing-free pipe pile obtained in the step S2 is 550-750 m 2 Per Kg; the fineness is less than or equal to 5 percent; median particle diameter (D) 50 ) 5-10 μm, the steam curing activity is more than or equal to 110 percent.
7. The preparation method of the mineral admixture for the steam-curing-free pipe pile as claimed in claim 1, wherein the mineral admixture comprises the following steps: the workability-improving additive of step S2 includes winnowing the first-grade ash and the microbeads.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211047342.XA CN115572091A (en) | 2022-08-29 | 2022-08-29 | Preparation method of steam-curing-free mineral admixture for pipe pile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211047342.XA CN115572091A (en) | 2022-08-29 | 2022-08-29 | Preparation method of steam-curing-free mineral admixture for pipe pile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115572091A true CN115572091A (en) | 2023-01-06 |
Family
ID=84580117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211047342.XA Pending CN115572091A (en) | 2022-08-29 | 2022-08-29 | Preparation method of steam-curing-free mineral admixture for pipe pile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115572091A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343151A (en) * | 2008-07-23 | 2009-01-14 | 宁波科环新型建材股份有限公司 | PHC pipe pile cement and preparation thereof |
| CN102765896A (en) * | 2012-07-30 | 2012-11-07 | 济南鲁新新型建材有限公司 | Mineral admixture for autoclave-free and steaming-free prestressed pipe piles and manufacturing method of mineral admixture |
| CN109020451A (en) * | 2018-10-09 | 2018-12-18 | 亚泰集团伊通水泥有限公司 | A kind of tubular pile cement and preparation method thereof |
| CN109437653A (en) * | 2018-11-16 | 2019-03-08 | 中国路桥工程有限责任公司 | A kind of scoria mineral admixture |
| CN110092630A (en) * | 2019-04-30 | 2019-08-06 | 山东盈润智能新材料有限公司 | A kind of PHC tubular pole admixture and its method for preparing PHC tubular pole |
| CN111099851A (en) * | 2019-12-23 | 2020-05-05 | 金泰成环境资源股份有限公司 | Autoclaving-free admixture for PHC (prestressed high strength concrete) pipe pile and method for preparing PHC pipe pile |
| CN111943548A (en) * | 2020-03-16 | 2020-11-17 | 江苏奥莱特新材料股份有限公司 | Steam-pressure-free concrete active powder for PHC pipe pile and preparation method thereof |
| CN112551934A (en) * | 2020-11-26 | 2021-03-26 | 江苏博拓新型建筑材料股份有限公司 | Non-autoclaved and non-autoclaved mineral admixture and preparation method thereof |
-
2022
- 2022-08-29 CN CN202211047342.XA patent/CN115572091A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343151A (en) * | 2008-07-23 | 2009-01-14 | 宁波科环新型建材股份有限公司 | PHC pipe pile cement and preparation thereof |
| CN102765896A (en) * | 2012-07-30 | 2012-11-07 | 济南鲁新新型建材有限公司 | Mineral admixture for autoclave-free and steaming-free prestressed pipe piles and manufacturing method of mineral admixture |
| CN109020451A (en) * | 2018-10-09 | 2018-12-18 | 亚泰集团伊通水泥有限公司 | A kind of tubular pile cement and preparation method thereof |
| CN109437653A (en) * | 2018-11-16 | 2019-03-08 | 中国路桥工程有限责任公司 | A kind of scoria mineral admixture |
| CN110092630A (en) * | 2019-04-30 | 2019-08-06 | 山东盈润智能新材料有限公司 | A kind of PHC tubular pole admixture and its method for preparing PHC tubular pole |
| CN111099851A (en) * | 2019-12-23 | 2020-05-05 | 金泰成环境资源股份有限公司 | Autoclaving-free admixture for PHC (prestressed high strength concrete) pipe pile and method for preparing PHC pipe pile |
| CN111943548A (en) * | 2020-03-16 | 2020-11-17 | 江苏奥莱特新材料股份有限公司 | Steam-pressure-free concrete active powder for PHC pipe pile and preparation method thereof |
| CN112551934A (en) * | 2020-11-26 | 2021-03-26 | 江苏博拓新型建筑材料股份有限公司 | Non-autoclaved and non-autoclaved mineral admixture and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1990410B (en) | Cement regeneration technique by activating discarded concrete | |
| CN103936363B (en) | Underwater concrete of a kind of containing limestone serous matter Machine-made Sand and preparation method thereof | |
| CN113307597B (en) | Nano recycled concrete, processing technology and application | |
| CN102718423B (en) | Preparation method of low-grade activated coal ash composite material | |
| CN101708985A (en) | Quick-hardening high-early strength concrete-based composite material for maritime work | |
| CN103224357A (en) | Green environmentally-friendly broken stone active powder concrete | |
| CN110526631A (en) | Fly ash-based geopolymer material and preparation method thereof for solidifying chromium slag | |
| CN107459311A (en) | A kind of preparation method of the wet-milling pulpous state admixture of the useless anti-folding toughness reinforcing of profit | |
| CN113248214A (en) | Machine-made sand ultrahigh-performance concrete with compressive strength of more than 180Mpa and preparation method thereof | |
| CN112125584A (en) | Preparation method of low-hydration-heat green self-leveling concrete | |
| CN107098642B (en) | High-strength self-compacting concrete | |
| CN105439485A (en) | Lithionite slag admixture and its preparation method and use | |
| CN115893895A (en) | Coagulation accelerating early strength agent, preparation method thereof and concrete composition | |
| CN114163207A (en) | High-strength low-elasticity hydraulic anti-abrasion concrete and preparation method thereof | |
| CN111320436A (en) | Design and preparation method of carbon nanotube panel concrete mixing proportion | |
| CN115432951A (en) | Preparation method of mineral admixture for commercial concrete | |
| CN111792905A (en) | Limestone tailing filling material and preparation method and application thereof | |
| CN115572091A (en) | Preparation method of steam-curing-free mineral admixture for pipe pile | |
| CN115594450B (en) | Geopolymer ceramsite lightweight concrete and preparation method thereof | |
| CN113955993B (en) | Low-cementing material self-compaction Yangtze river dredging superfine sand concrete | |
| CN116715497A (en) | Carbon-fixing aerated concrete wall material product based on nickel slag and concrete tail slurry and preparation method thereof | |
| CN103896531B (en) | Mix high-strength concrete tubular pile and the production method thereof of levigate rice hull ash | |
| CN115490449A (en) | Preparation method of superfine mineral admixture | |
| CN109265126A (en) | A method of grouting material is prepared using discarded clay brick | |
| CN101823847B (en) | Gelled material for improving properties of fly ash-based inorganic polymer and preparation method thereof |
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 |