CN114920528B - Inorganic artificial stone plate with antibacterial effect and preparation method thereof - Google Patents

Inorganic artificial stone plate with antibacterial effect and preparation method thereof Download PDF

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CN114920528B
CN114920528B CN202210516174.8A CN202210516174A CN114920528B CN 114920528 B CN114920528 B CN 114920528B CN 202210516174 A CN202210516174 A CN 202210516174A CN 114920528 B CN114920528 B CN 114920528B
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parts
artificial stone
inorganic artificial
pyrithione
antibacterial effect
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CN114920528A (en
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胡浩
高红刚
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Jingzhou Fanshi Creative Technology Co ltd
Guangdong Fanshi Creative Technology Co ltd
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Jingzhou Fanshi Creative Technology Co ltd
Guangdong Fanshi Creative Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08Slag cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/128Heterocyclic nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/2092Resistance against biological degradation
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The invention discloses an inorganic artificial stone board with an antibacterial effect and a preparation method thereof, wherein cement, bentonite, modified pyrithione salt powder, a surfactant, quartz sand and water are used as raw materials, and a small amount of modified pyrithione salt powder is added, so that the prepared inorganic artificial stone board can effectively inhibit bacteria and mould on the surface of the board; the sodium bentonite can improve the viscosity of the slurry and meet the viscosity requirement of the inorganic artificial stone board; the inorganic artificial stone slab has the advantages of simple preparation process, good antibacterial and mildew-proof effects and lasting action time, and can meet the daily production and living requirements.

Description

Inorganic artificial stone plate with antibacterial effect and preparation method thereof
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to an inorganic artificial stone board with an antibacterial effect and a preparation method thereof.
Background
In recent years, with the repeated occurrence of viruses, people pay more attention to the antibacterial performance of building materials, and particularly, the antibacterial agent is applied to building materials in public building fields such as subways, hotels, hospitals and the like.
The existing common inorganic artificial stone plate on the market has low density, is easy to absorb moisture and absorb water and propagate bacteria, mildew, change color and the like, and is a strong alkaline material, so that the common antibacterial agent is quickly decomposed in the strong alkaline material and cannot be stably present in the artificial stone plate, and the antibacterial effect cannot be achieved.
Therefore, the antibacterial building materials have become an indispensable member in the field of building decoration, the antibacterial mode mainly adopts the addition of antibacterial agents and the building materials have certain antibacterial performance, the use, development and application of the antibacterial agents are the most extensive, and the antibacterial effect is the most obvious, but the metal antibacterial agents have the defects of oxidative discoloration, pollution and body injury caused by organic antibacterial agents and instability of natural antibacterial agents, and the building materials are required to be improved and enhanced by utilizing different antibacterial base materials and different antibacterial mechanisms. Through a great deal of researches, the invention finally finds out a material suitable for matching, combines the production process, improves the product density, reduces the water absorption rate and produces the inorganic artificial stone board with the antibacterial and mildew-proof effects.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide the inorganic artificial stone board with the antibacterial effect.
In order to solve the technical problems, the invention provides the following technical scheme: comprising the steps of (a) a step of,
cement, bentonite, modified pyrithione salt powder, surfactant, quartz sand and water;
wherein, the weight portions of the inorganic artificial stone slab are 20 to 30 portions of cement, 5 to 15 portions of bentonite, 1 to 3 portions of modified pyrithione salt powder, 0.5 to 1.5 portions of surfactant, 40 to 60 portions of quartz sand and 8 to 15 portions of water.
As a preferred embodiment of the present invention, wherein: the cement is slag silicate cement, wherein the addition amount of granulated blast furnace slag in the cement is 20-30%.
As a preferred embodiment of the present invention, wherein: the bentonite is sodium bentonite, wherein the mesh number of the bentonite is 1000-2000 mesh.
As a preferred embodiment of the present invention, wherein: the modified pyrithione salt powder comprises one or more of modified copper pyrithione, modified zinc pyrithione, modified sodium pyrithione, modified lithium pyrithione and modified magnesium pyrithione.
As a preferred embodiment of the present invention, wherein: the surfactant is one or two of anionic surfactant and nonionic surfactant.
As a preferred embodiment of the present invention, wherein: the anionic surfactant is one or more of sodium fatty alcohol-polyoxyethylene ether sulfate, sodium dodecyl sulfate and sodium fatty alcohol-polyoxyethylene ether carboxylate; the nonionic surfactant is one or more of fatty acid polyoxyethylene ester and polyoxyethylene alkylamine.
As a preferred embodiment of the present invention, wherein: the quartz sand is superfine quartz sand, wherein the mesh number of the quartz sand is more than 200 meshes.
As a preferred embodiment of the present invention, wherein: the water: and (3) cement: the mass ratio of the quartz sand is 1: 2-3: 4 to 6.
It is still another object of the present invention to provide a method for preparing an inorganic artificial stone board having an antibacterial effect.
In order to solve the technical problems, the invention provides the following technical scheme: comprising the steps of (a) a step of,
preparing modified pyrithione salt powder: dispersing 20-30 parts of pyrithione salt particles in 200 parts of deionized water, heating to 50-80 ℃ after rapid stirring, adding 0.5-1.5 parts of quaternary ammonium salt, continuously stirring, standing and cooling to room temperature after dispersion, filtering to obtain filter residues, drying at 60 ℃ in an oven, crushing and sieving to obtain surface modified pyrithione salt powder;
mixing and stirring 20-30 parts of cement and 4-8 parts of water, sequentially adding 40-60 parts of quartz sand, 0.5-1 part of surfactant, 5-15 parts of bentonite and 1-1.5 parts of modified pyrithione salt powder, fully stirring uniformly by adding 4-8 parts of water, uniformly spreading the mixed materials by a material distributor, pressing and forming by a press, and binding, polishing for 96 hours after curing to obtain the inorganic artificial stone board with an antibacterial effect.
As a preferred embodiment of the present invention, wherein: the quaternary ammonium salt is one or more of dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium formate, hexadecyl trimethyl ammonium acetate and hexadecyl trimethyl ammonium butyrate.
The invention has the beneficial effects that:
(1) The inorganic artificial stone plate prepared by the invention is added with a small amount of modified pyrithione salt powder, so that bacteria and mould on the surface of the plate can be effectively inhibited.
(2) The sodium bentonite adopted by the invention can improve the viscosity of slurry, meet the viscosity requirement of inorganic artificial stone plates, and simultaneously has good adsorption performance and cation exchange capacity, and can cooperate with metal ions in modified pyrithione salt powder to improve the antibacterial stability of the stone plates.
(3) The invention optimizes the proportion of cement, quartz sand and water, so that the prepared stone slab has good stability and compressive strength.
(4) The inorganic artificial stone slab has the advantages of simple preparation process, good antibacterial and mildew-proof effects and lasting action time, and can meet the daily production and living requirements.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
fig. 1 is a flow chart of the preparation of the inorganic artificial stone board with the antibacterial effect.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The materials used in the invention:
and (3) cement: the Beijing mountain hydrologic source novel building materials are commonly sold in the market; bentonite: the Jinan Ming chemical industry Co., ltd, is commonly sold in the market; pyrithione salts, shandong Linguan fine chemical Co., ltd, are commercially available in general; surfactants, shandong non-line technologies Co., ltd, are commonly commercially available; quartz sand, hebei UFOR building materials science and technology Co., ltd, is commonly sold in the market; quaternary ammonium salt, jinan Baoli chemical industry Co., ltd, is commonly sold in the market.
The antibacterial performance of the invention is measured according to JC/T897-2014 antibacterial performance of antibacterial ceramic products;
the mildew resistance of the invention is measured according to GB/T35469-2017 building wood-plastic composite mildew resistance test method;
the water absorption and bending strength of the invention are measured according to GB/T19766-2016 Natural Marble building Board.
Example 1
Dispersing 15 parts of zinc pyrithione and 15 parts of copper pyrithione particles in 200 parts of deionized water, heating to 60 ℃ after rapid stirring, adding 1 part of cetyltrimethylammonium formate, continuously stirring, standing and cooling to room temperature after dispersion, filtering to obtain filter residues, drying at 60 ℃ in an oven, crushing and sieving to obtain surface modified zinc pyrithione and copper pyrithione mixed powder;
mixing and stirring 25 parts of cement and 6 parts of water, sequentially adding 50 parts of quartz sand, 1 part of fatty alcohol polyoxyethylene ether sodium sulfate, 10 parts of bentonite and 2 parts of modified pyrithione salt powder, adding 6 parts of water, fully and uniformly stirring, uniformly spreading the mixed materials by a material distributor, pressing and forming by a press, and performing thickness binding and polishing for 96 hours after curing to obtain the inorganic artificial stone plate with an antibacterial effect.
Example 2
In this example, compared with example 1, 30 parts of copper pyrithione, zinc pyrithione, sodium pyrithione, lithium pyrithione, and magnesium pyrithione were each dispersed in 200 parts of deionized water in the preparation of modified pyrithione salt powder, and the other preparation processes were the same as in example 1.
Table 1 shows the results of measuring the antibacterial and antifungal properties of the stone slabs prepared in example 1 and example 2.
TABLE 1
Figure BDA0003639531030000041
Example 3
In this example, compared with example 1, in the preparation of the modified pyrithione salt powder, the quaternary ammonium salt was replaced with dodecyltrimethylammonium chloride, dodecyldimethylbenzyl ammonium chloride, cetyltrimethylammonium acetate and cetyltrimethylammonium butyrate, respectively, and the other preparation processes were the same as in example 1.
Table 2 shows the results of measuring the antibacterial and antifungal properties of the stone slabs prepared in example 1 and example 3.
TABLE 2
Figure BDA0003639531030000051
Example 4
In this example, compared with example 1, the surfactant was replaced with sodium dodecyl sulfate, sodium fatty alcohol-polyoxyethylene ether carboxylate, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine, respectively, and the other preparation processes were the same as in example 1.
Table 3 shows the results of measuring the antibacterial and antifungal properties of the stone slabs prepared in example 1 and example 4.
TABLE 3 Table 3
Figure BDA0003639531030000052
Example 5
Dispersing 15 parts of zinc pyrithione and 15 parts of copper pyrithione particles in 200 parts of deionized water, heating to 60 ℃ after rapid stirring, adding 1 part of cetyltrimethylammonium formate, continuously stirring, standing and cooling to room temperature after dispersion, filtering to obtain filter residues, drying at 60 ℃ in an oven, crushing and sieving to obtain surface modified zinc pyrithione and copper pyrithione mixed powder;
mixing and stirring 25 parts of cement and 6 parts of water, sequentially adding 50 parts of quartz sand, 10 parts of bentonite and 2 parts of modified pyrithione salt powder, adding 6 parts of water, fully stirring uniformly, spreading the mixed materials uniformly by a spreader, pressing and forming by a press, curing for 96 hours, and performing thickness binding and polishing to obtain the inorganic artificial stone board with an antibacterial effect.
Example 6
Mixing and stirring 25 parts of cement and 6 parts of water, sequentially adding 50 parts of quartz sand, 1 part of fatty alcohol polyoxyethylene ether sodium sulfate, 10 parts of bentonite, 1 part of zinc pyrithione and 1 part of copper pyrithione particles, adding 6 parts of water, fully and uniformly stirring, uniformly spreading the mixed materials by a distributing machine, pressing and forming by a pressing machine, and carrying out thickness binding and polishing for 96 hours after curing to obtain the inorganic artificial stone plate with an antibacterial effect.
Example 7
Dispersing 15 parts of zinc pyrithione and 15 parts of copper pyrithione particles in 200 parts of deionized water, heating to 60 ℃ after rapid stirring, adding 1 part of cetyltrimethylammonium formate, continuously stirring, standing and cooling to room temperature after dispersion, filtering to obtain filter residues, drying at 60 ℃ in an oven, crushing and sieving to obtain surface modified zinc pyrithione and copper pyrithione mixed powder;
mixing and stirring 25 parts of cement and 6 parts of water, sequentially adding 50 parts of quartz sand, 1 part of fatty alcohol polyoxyethylene ether sodium sulfate and 2 parts of modified pyrithione salt powder, adding 6 parts of water, fully stirring uniformly, spreading the mixed materials uniformly by a spreader, pressing and forming by a press, curing for 96 hours, and performing thickness binding and polishing to obtain the inorganic artificial stone plate with an antibacterial effect.
Example 8
Dispersing 15 parts of zinc pyrithione and 15 parts of copper pyrithione particles in 200 parts of deionized water, heating to 60 ℃ after rapid stirring, adding 1 part of cetyltrimethylammonium formate, continuously stirring, standing and cooling to room temperature after dispersion, filtering to obtain filter residues, drying at 60 ℃ in an oven, crushing and sieving to obtain surface modified zinc pyrithione and copper pyrithione mixed powder;
mixing and stirring 25 parts of cement and 6 parts of water, sequentially adding 50 parts of quartz sand, 3 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 10 parts of bentonite and 2 parts of modified pyrithione salt powder, adding 6 parts of water, fully and uniformly stirring, uniformly spreading the mixed materials by a material distributor, pressing and forming by a press, and performing thickness binding and polishing for 96 hours after curing to obtain the inorganic artificial stone plate with an antibacterial effect.
Example 9
Dispersing 15 parts of zinc pyrithione and 15 parts of copper pyrithione particles in 200 parts of deionized water, heating to 60 ℃ after rapid stirring, adding 1 part of cetyltrimethylammonium formate, continuously stirring, standing and cooling to room temperature after dispersion, filtering to obtain filter residues, drying at 60 ℃ in an oven, crushing and sieving to obtain surface modified zinc pyrithione and copper pyrithione mixed powder;
mixing and stirring 25 parts of cement and 6 parts of water, sequentially adding 50 parts of quartz sand, 1 part of fatty alcohol polyoxyethylene ether sodium sulfate, 10 parts of bentonite and 5 parts of modified pyrithione salt powder, adding 6 parts of water, fully and uniformly stirring, uniformly spreading the mixed materials by a material distributor, pressing and forming by a press, and performing thickness binding and polishing for 96 hours after curing to obtain the inorganic artificial stone plate with an antibacterial effect.
Table 4 shows the results of measuring the antibacterial and antifungal properties of the stone slabs prepared in example 1 and examples 5 to 9.
TABLE 4 Table 4
Figure BDA0003639531030000071
Table 5 shows the results of measuring the water absorption and the compression resistance of the stone slabs prepared in example 1 and examples 5 to 9.
TABLE 5
Measurement index Example 1 Example 5 Example 6 Example 7 Example 8 Example 9
Water absorption rate 0.2% 1.1% 0.9% 1.4% 0.65% 0.8%
Flexural Strength 12Mpa 7Mpa 8Mpa 6Mpa 9Mpa 10Mpa
The inorganic artificial stone plate prepared by the invention is added with a small amount of modified pyrithione salt powder, so that the antibacterial and mildew-proof effects of the plate are greatly enhanced, and because metal cations contained in the modified pyrithione salt powder can be combined with negatively charged heads of phospholipid molecules on the surfaces of proteins/enzymes in bacteria and microorganisms, cell membranes are damaged, cell division and replication are disturbed, and bacterial growth is inhibited.
The invention adopts bentonite to improve the viscosity of slurry, the compactness and the hydrophobicity of the inorganic artificial board, the water absorption of the stone board can be reduced, and simultaneously, the bentonite can be synergistic with the modified pyrithione salt, because the bentonite has outstanding cation exchange capacity and good adsorption performance, and the antibacterial stability of the stone board can be obviously improved by introducing the modified pyrithione salt between bentonite layers.
According to the invention, a small amount of surfactant is added into the stone slab, on one hand, the added surfactant can form a compound system with quaternary ammonium salt in pyrithione salt, so that the antibacterial and mildew-proof properties of the slab are better; on the other hand, as the compound system formed by the surfactant and the quaternary ammonium salt can act with quartz sand in the raw materials, the system forms double-layer adsorption on the surface of the quartz sand to hydrophobize the quartz sand, so that the hydrophobicity of the plate is lower.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.

Claims (5)

1. An inorganic artificial stone board with antibacterial effect, which is characterized in that: comprising the steps of (a) a step of,
20-30 parts of cement, 5-15 parts of bentonite, 1-3 parts of modified pyrithione salt powder, 0.5-1.5 parts of surfactant, 40-60 parts of quartz sand and 8-15 parts of water;
wherein the modifier of the modified pyrithione salt powder is cetyl trimethyl ammonium formate, and the pyrithione salt powder is compounded by copper pyrithione and zinc pyrithione according to the proportion of 1:1; the surfactant is sodium fatty alcohol polyoxyethylene ether sulfate.
2. An inorganic artificial stone board with antibacterial effect as claimed in claim 1, wherein: the cement is slag silicate cement, wherein the addition amount of granulated blast furnace slag in the cement is 20% -30%.
3. An inorganic artificial stone board with antibacterial effect as claimed in claim 1, wherein: the bentonite is sodium bentonite, wherein the mesh number of the bentonite is 1000-2000 mesh.
4. An inorganic artificial stone board with antibacterial effect as claimed in claim 1, wherein: the quartz sand is superfine quartz sand, wherein the mesh number of the quartz sand is more than 200 meshes.
5. An inorganic artificial stone board with antibacterial effect as claimed in claim 1, wherein: the water: and (3) cement: the mass ratio of the quartz sand is 1: 2-3: 4-6.
CN202210516174.8A 2022-05-12 2022-05-12 Inorganic artificial stone plate with antibacterial effect and preparation method thereof Active CN114920528B (en)

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JP4291543B2 (en) * 2002-03-29 2009-07-08 三洋化成工業株式会社 Antibacterial and antifungal agent for cement
US6893752B2 (en) * 2002-06-28 2005-05-17 United States Gypsum Company Mold-resistant gypsum panel and method of making same
CN106116458B (en) * 2016-06-25 2018-12-28 王赞 Antibacterial Antique Imitation Tiles and preparation method thereof
HUP1800035A1 (en) * 2018-01-30 2019-08-28 Sanex Pro Kft Antimicrobial composite a process for the manufacture thereof and application of the composite
KR102348646B1 (en) * 2021-05-31 2022-01-12 흥덕산업 주식회사 Organic-inorganic hybrid antibacterial concrete block with surface layer using acryl resin and antibacterial artificial aggregate and the manufacturing method thereof

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