WO2020228432A1 - 一种用于3d打印建筑的防水保温砂浆及其制备方法和应用 - Google Patents

一种用于3d打印建筑的防水保温砂浆及其制备方法和应用 Download PDF

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WO2020228432A1
WO2020228432A1 PCT/CN2020/082021 CN2020082021W WO2020228432A1 WO 2020228432 A1 WO2020228432 A1 WO 2020228432A1 CN 2020082021 W CN2020082021 W CN 2020082021W WO 2020228432 A1 WO2020228432 A1 WO 2020228432A1
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Prior art keywords
waterproof
thermal insulation
insulation mortar
powder
cement
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PCT/CN2020/082021
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English (en)
French (fr)
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钱元弟
尹万云
金仁才
雷团结
胡义
王孝平
王慧
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中国十七冶集团有限公司
马鞍山十七冶工程科技有限责任公司
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Priority to MYPI2020004437A priority Critical patent/MY190753A/en
Publication of WO2020228432A1 publication Critical patent/WO2020228432A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions 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
    • C04B28/06—Aluminous cements
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00293—Materials impermeable to liquids
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

  • the invention belongs to the technical field of new building wall materials, and in particular relates to a waterproof and thermal insulation mortar for 3D printing buildings, and a preparation method and application thereof.
  • New buildings strictly implement the architectural design standards, and cities where conditions permit are the first to implement the energy-saving rate of 65%.
  • existing self-insulating blocks usually have various disadvantages such as excessive investment in equipment, high labor costs, high energy consumption, serious environmental pollution, complex construction techniques, long construction period, high cost, and more cold and hot bridges.
  • 3D printing is widely used in various research fields, has a huge impact on traditional social production, and has become a creative technology that changes the future.
  • 3D printing concrete technology based on 3D printing is a major turning point in the history of concrete development.
  • 3D printing walls have been developing rapidly due to their good wall quality, fast construction speed, time saving, moderate cost, and good integrity.
  • mortar is one of the core materials in 3D printing wall materials.
  • Mechanical properties such as strength, fluidity and curing rate of the mortar also put forward higher requirements, that is, the mortar for 3D printing is required to flow well in the pumping tube, and it can be cured quickly after printing from the print head.
  • the Chinese patent application number 201610614696.6 discloses a new type of high-strength and high-toughness waterproof mortar material that can be used for 3D architectural printing and a preparation method thereof.
  • the waterproof mortar material in this application is composed of cement, sand, polypropylene fiber, and polymer. It is composed of ethylene fiber, basalt fiber, HPMC cellulose, fly ash, water reducing agent, defoamer, air-entraining agent, organic silicon waterproofing agent, redispersible latex powder and water.
  • the application can improve the mechanical strength and waterproof performance of the mortar material for 3D architectural printing to a certain extent, but the fluidity and curing rate controllability of the obtained mortar still need to be further improved.
  • the application of Chinese Patent Application No. 201610307917.5 discloses a 3D printing mortar and its preparation method.
  • the 3D printing mortar of this application is mainly composed of 70%-90% compound cement and 5%-20% quartz sand. Lime 0.2%-2%, coagulant 1%-5%, water reducer 0%-3%, defoamer 0%-3%, thickener 0%-0.5% and fiber 0.2-0.8%,
  • the component formula of the mortar is optimized, which can effectively improve the fluidity and construction performance of the mortar, but its waterproof and thermal insulation performance still needs to be further improved.
  • the purpose of the present invention is to overcome the difficulty of existing mortars to meet the requirements of 3D printing buildings for waterproof performance, mechanical properties, fluidity and curing at the same time, and to provide a waterproof and thermal insulation mortar for 3D printing buildings and a preparation method thereof.
  • the technical scheme of the present invention can effectively improve the mechanical properties, fluidity and curing rate of the mortar on the basis of ensuring the waterproof and thermal insulation performance of the mortar, thereby meeting the requirements of 3D printing buildings.
  • a waterproof and thermal insulation mortar for 3D printed buildings of the present invention its raw materials include the following components by mass percentage:
  • the composite cement is composed of low-alkalinity sulfoaluminate cement and ultrafine cement, wherein the ultrafine cement accounts for 30-55% of the total composite cement.
  • the average particle size of the ultra-fine cement is 1-4 ⁇ m, of which more than 85% of the particles are below 4 ⁇ m in size, and the specific surface area is 1200-2200 m 2 /kg.
  • the filler adopts iron tailing slag powder, blast furnace slag powder or lead-zinc tailing slag powder, with a particle size of 3.5 ⁇ m-7.5 ⁇ m, and the hollow vitrified beads have a particle size of 0.8-2.5 mm,
  • the density is 50-200 kg/m 3
  • the particle size of the expanded vermiculite powder is 0.3-0.6 mm
  • the density is 60-180 kg/m 3 .
  • the length of the straw fiber is 1-1.7mm
  • the density is 400-500kg/m 3
  • the length of the imitation steel fiber is 3-8mm
  • the density is 0.7-0.85g/cm 3
  • the initial modulus It is 9-12GPa
  • the elongation at break is 32%-38%.
  • the composite penetrant is composed of calcium sodium ethylenediaminetetraacetate, cast stone powder and ⁇ -type hemihydrate, wherein the mass ratio of calcium sodium ethylenediaminetetraacetate, cast stone powder and ⁇ -type hemihydrate is ( 2-3):1:(2-2.5).
  • the curing agent is composed of polythiol and calcium oxide, the mass ratio of polythiol to calcium oxide is 4:1-6:1, and the content of the curing agent is 0.5-2% of the total composite cement .
  • the redispersible latex powder is vinyl acetate and higher fatty acid vinyl ester copolymer rubber powder;
  • the water reducing agent is a polycarboxylic acid water reducing agent or aliphatic hydroxysulfonate condensate superplasticizer .
  • the preparation method of waterproof and thermal insulation mortar for 3D printed buildings of the present invention includes the following steps: placing low-alkalinity sulphoaluminate cement and ultra-fine cement in a mixing device and mixing for 3 to 5 minutes, and then press the quality Add filler, hollow vitrified microbeads, and expanded vermiculite powder to it and continue to stir for 5-7 minutes, then put in the redispersible latex powder and stir for 2 to 4 minutes; continue to put the compound penetrant and defoamer into the mixing equipment Mix with water reducing agent for 7-10 minutes; finally put in the imitated steel fiber and straw fiber, and continue to mix for 9-12 minutes to obtain the dry powder of waterproof thermal insulation mortar.
  • the application of the waterproof and thermal insulation mortar for 3D printed buildings of the present invention is to directly apply the waterproof and thermal insulation mortar to 3D printed buildings.
  • the dry powder of the waterproof thermal insulation mortar and curing agent are put into automatic mixing and spraying integration In the equipment, stir for 4-5 minutes, then add appropriate amount of water to stir and then spray construction, where the weight ratio of the added water to the dry powder is 1:1 ⁇ 3, preferably 1:1.6, add water and stir until the consistency is 85 ⁇ 102mm, preferably the consistency is 96mm.
  • the waterproof and thermal insulation mortar used in 3D printing buildings of the present invention is designed by optimizing its raw material components and proportions, so that on the one hand, the waterproof and impermeability performance of the mortar can be improved, and the waterproof performance of the interior and exterior walls of the building can be improved.
  • the demand for impermeability on the other hand, it can effectively improve the fluidity of the mortar, realize the rapid curing and controllability of the mortar, and then meet the demand for the use of 3D printed buildings.
  • a waterproof and thermal insulation mortar for 3D printed buildings of the present invention Its composite cement is composed of low-alkalinity sulfoaluminate cement and ultrafine cement. Compound, and optimize the design of its compound ratio, so as to meet the requirements of 3D printing construction mortar for strength and impermeability.
  • a curing agent with a specific composition and ratio through the common and coordinated effect of the curing agent and the ultrafine cement, the rapid curing and controllability of the inorganic and organic components can be realized, and the stability of the mortar material in the early stage can be ensured.
  • it can effectively realize the rapid and stable increase of the strength of the mortar in the later stage, and ensure the subsequent printing quality.
  • the waterproof and thermal insulation mortar for 3D printing buildings of the present invention is optimized by adding expanded vermiculite powder and hollow vitrified microspheres to it, and optimizes the particle size distribution of filler, hollow vitrified microspheres and vermiculite powder , Through the good particle gradation between the three, which can effectively improve the strength and strength stability of the mortar.
  • the waterproof and thermal insulation mortar used in 3D printing buildings of the present invention by adding a composite penetrant to it, and optimizing the composition and ratio of its components, through calcium sodium ethylenediaminetetraacetate, cast stone powder It has a compound effect with ⁇ -type semi-hydrated gypsum, and works together with composite cement and fillers, which can further improve the impermeability and waterproof performance of the mortar, so that the waterproof effect and mechanical strength are optimally matched.
  • the present invention has a good water-reducing effect, does not entrain air, and basically has no effect on the setting time. At the same time, it has good adaptability to cement and can be used in combination with other various additives.
  • the preparation method of the waterproof and thermal insulation mortar for 3D printed buildings of the present invention by optimizing the components, proportions and specific preparation process of the waterproof thermal insulation mortar, can meet the requirements of the waterproof and thermal insulation effect of the building mortar. On the basis of the mortar, it can effectively improve the flow properties of the mortar, increase its curing rate, and further improve its mechanical properties, so as to meet the needs of 3D printed buildings.
  • Figure 1 is the performance comparison data of the mortars in the various examples and comparative examples of the present invention.
  • the present invention can effectively solve the problem that the existing mortar cannot meet the requirements of 3D printing buildings for waterproof and impermeable performance, mechanical properties, and flow and curing.
  • the composite addition of calcium sodium ethylenediaminetetraacetate, cast stone powder and ⁇ -type hemihydrate gypsum can effectively improve the double-sided waterproof and impermeability properties of the mortar material.
  • the composite penetrant and filler have low alkalinity
  • the combined effect of the sulphoaluminate cement/superfine cement compound cement can also effectively increase the strength of the obtained mortar material and ensure the best combination of its waterproof performance and mechanical strength.
  • the present invention can realize the rapid and controllable curing of inorganic and organic components, and ensure the stability of the mortar materials in the early stage.
  • the combined effect of cement can also effectively achieve the rapid and stable increase in the strength of the mortar in the later stage, ensuring the quality of subsequent printing.
  • the curing agent of the present invention can perform curing and shaping in 3-6 minutes, and its lowest temperature is -5°C.
  • the calcium oxide reacts with water and generates heat to assist in rapid curing, and also assist in the waterproof and impermeable properties of the composite penetrant Strengthen the role.
  • the filler of the present invention adopts iron tailing slag powder, blast furnace slag powder or lead-zinc tailing slag powder, the particle size of which is 3.5 ⁇ m-7.5 ⁇ m, the particle size of hollow vitrified beads is 0.8-2.5mm, and the density is 50-200kg/ m 3 , the particle size of the expanded vermiculite powder is 0.3-0.6mm, and the density is 60-180kg/m 3.
  • a waterproof and thermal insulation mortar for 3D printed buildings its raw materials include the following components by mass percentage:
  • the composite cement of this embodiment is composed of low-alkalinity sulfoaluminate cement and ultra-fine cement.
  • the ultra-fine cement accounts for 30% of the total composite cement.
  • the composite penetrant is composed of calcium sodium ethylenediaminetetraacetate and cast stone powder.
  • ⁇ -type hemihydrate gypsum wherein the mass ratio of sodium ethylenediaminetetraacetate, cast stone powder and ⁇ -type hemihydrate gypsum is 2:1:2;
  • the curing agent is composed of polythiol and calcium oxide, and the mass ratio of polysulfide
  • the mass ratio of alcohol to calcium oxide is 4:1, and the content of curing agent is 0.5% of the total composite cement.
  • the redispersible latex powder is vinyl acetate and higher fatty acid vinyl ester copolymer rubber powder; the water-reducing agent is a polycarboxylic acid-based water-reducing agent, and the filler is fine iron tailings slag powder.
  • the preparation method of waterproof and thermal insulation mortar for 3D printed buildings in this embodiment includes the following steps: placing low-alkalinity sulphoaluminate cement and ultra-fine cement in a mixing device for 3 minutes, and then mixing them in a mass ratio. Add filler, hollow vitrified microbeads, and expanded vermiculite powder and continue to stir for 7 minutes, then add the redispersible latex powder and stir for 4 minutes; continue to add compound penetrant, defoamer and water reducing agent into the mixing equipment, and stir for 7 minutes ; Finally, put in the imitation steel fiber and straw fiber, and continue to stir for 12 minutes to obtain the waterproof and thermal insulation mortar dry powder.
  • the waterproof and thermal insulation mortar obtained in this example is directly applied to a 3D printed building. Specifically, the dry powder of the waterproof thermal insulation mortar and the curing agent are put into the automatic mixing and spraying integrated equipment, stirring for 4-5 minutes, and then adding an appropriate amount of water. Just spray construction, where the weight ratio of the added water to the dry powder is 1:3, add water and stir until the consistency is 102mm.
  • a waterproof and thermal insulation mortar for 3D printed buildings its raw materials include the following components by mass percentage:
  • the composite cement of this embodiment is composed of low-alkalinity sulfoaluminate cement and ultra-fine cement.
  • the ultra-fine cement accounts for 43% of the total composite cement.
  • the composite penetrant is composed of calcium sodium ethylenediaminetetraacetate and cast stone powder.
  • ⁇ -type hemihydrate gypsum in which the mass ratio of calcium sodium ethylenediaminetetraacetate, cast stone powder and ⁇ -type hemihydrate gypsum is 3:1:2.5;
  • the curing agent is composed of polythiol and calcium oxide, polysulfide
  • the mass ratio of alcohol to calcium oxide is 5:1, and the content of curing agent is 1.3% of the total composite cement.
  • the vinyl acetate and higher fatty acid vinyl ester copolymer rubber powder, the water reducing agent is an aliphatic hydroxysulfonate condensate superplasticizer, and the filler adopts blast furnace slag powder.
  • the preparation method of waterproof and thermal insulation mortar for 3D printed buildings in this embodiment includes the following steps: placing low-alkalinity sulphoaluminate cement and ultrafine cement in a mixing device for 5 minutes, and then mixing them in a mass ratio. Add filler, hollow vitrified microbeads, and expanded vermiculite powder and continue to stir for 5 minutes, then add the redispersible latex powder and stir for 2 minutes; continue to add compound penetrant, defoamer and water reducing agent into the mixing equipment, and stir for 10 minutes ; Finally, put in the imitation steel fiber and straw fiber, and continue to stir for 9 minutes to obtain the waterproof and thermal insulation mortar dry powder.
  • the waterproof and thermal insulation mortar obtained in this example is directly applied to a 3D printed building. Specifically, the dry powder of the waterproof thermal insulation mortar and the curing agent are put into the automatic mixing and spraying integrated equipment, stirring for 4-5 minutes, and then adding an appropriate amount of water. Just spray construction, where the weight ratio of the added water to the dry powder is 1:1, add water and stir until the consistency is 85mm.
  • a waterproof and thermal insulation mortar for 3D printed buildings its raw materials include the following components by mass percentage:
  • the composite cement of this embodiment is composed of low-alkalinity sulfoaluminate cement and ultrafine cement.
  • the ultrafine cement accounts for 55% of the total composite cement.
  • the composite penetrant is composed of calcium sodium ethylenediaminetetraacetate and cast stone powder.
  • ⁇ -type hemihydrate gypsum in which the mass ratio of calcium sodium ethylenediaminetetraacetate, cast stone powder and ⁇ -type hemihydrate gypsum is 2.5:1:2.2;
  • the curing agent is composed of polythiol and calcium oxide, polysulfide
  • the mass ratio of alcohol to calcium oxide is 6:1, and the content of curing agent is 2% of the total composite cement.
  • the redispersible latex powder is vinyl acetate and higher fatty acid vinyl ester copolymer rubber powder
  • the water reducing agent is a polycarboxylic acid water reducing agent
  • the filler is lead-zinc tailing slag powder.
  • the preparation method of waterproof and thermal insulation mortar for 3D printed buildings in this embodiment includes the following steps: placing low-alkalinity sulphoaluminate cement and ultra-fine cement in a mixing device for 4 minutes, and then mixing them according to the mass ratio. Add filler, hollow vitrified microbeads, and expanded vermiculite powder and continue to stir for 6 minutes, then add redispersible latex powder and stir for 3 minutes; continue to add compound penetrant, defoamer and water reducing agent into the mixing equipment, and stir for 8 minutes ; Finally, put in the imitation steel fiber and straw fiber and continue to stir for 10 minutes to obtain the waterproof and thermal insulation mortar dry powder.
  • the waterproof and thermal insulation mortar obtained in this example is directly applied to a 3D printed building. Specifically, the dry powder of the waterproof thermal insulation mortar and the curing agent are put into the automatic mixing and spraying integrated equipment, stirring for 4-5 minutes, and then adding an appropriate amount of water. Just spray construction, where the weight ratio of the added water to the dry powder is 1:1.6, add water and stir until the consistency is 96mm.
  • the weight percentage of each component in the mortar of this comparative example is as follows:
  • the aforementioned composite penetrant includes calcium hydroxide, ethylenediamine tetraacetic acid and powdered instant sodium fluorosilicate, the weight percentages of which are 1.2%, 1.4% and 0.6%, respectively.
  • the composition of the filler and the curing agent is the same as that of Example 1.
  • the weight percentage of each component of this comparative example is:
  • the weight percentage of each component of this comparative example is:

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Abstract

一种用于3D打印建筑的防水保温砂浆及其制备方法和应用，其原材料包括如下质量百分比的组分：复合水泥50-80％，填料10-20％，中空玻化微珠5-21％，膨胀蛭石粉0.2-0.4％，秸秆纤维0.1-0.3％，仿钢纤维0.05-0.4％，复合渗透剂1.8-5.3％，固化剂0.2-2％，消泡剂0.1-0.5％，可再分散乳胶粉0.3-0.7％，减水剂0.5-0.8％。

Description

一种用于3D打印建筑的防水保温砂浆及其制备方法和应用 技术领域
本发明属于新型建筑墙体材料技术领域，尤其是涉及一种用于3D打印建筑的防水保温砂浆及其制备方法和应用。
背景技术
近年来国家对节约能源，改善居住条件非常重视，建筑节能是我国节能工作的一个重要领域。十七大报告中提出了“建设生态文明，必须形成有利于节约能源资源和保护生态环境的城乡建设模式和消费模式”，2005年以来，国家有关部门出台的一系列文件对建筑节能提出了新的要求，新建建筑要向强制执行国家已颁布的建筑节能设计标准推进，逐步提高新型墙体材料的生产和应用比例，增加节能建筑面积。新建建筑严格执行建筑设计标准，有条件的城市率先执行节能率65％的标准。但现有自保温砌块通常存在设备投资过大、人工成本高、能源消耗高、环境污染严重、施工工艺复杂、施工工期长、造价偏高、冷热桥较多等各种弊端。
3D打印作为第三次工业革命的重要标志，广泛应用于各个研究领域，对传统社会生产产生了巨大冲击，成为改变未来的创造性技术。以3D打印为基础的3D打印混凝土技术作为一种新型技术，是混凝土发展史上的一个重大转折点。3D打印墙体由于墙体质量好、施工速度快、节约工期、造价适中、整体性好而得到快速发展。其中砂浆是3D打印墙体材料中的核心材料之一，为满足3D打印的需求，相对于现有普通砂浆而言除了要求内外墙体要具有更好的防水效果，同时对3D打印用砂浆的强度等力学性能以及砂浆的流动性和固化速率也提出了更高的要求，也即要求3D打印用砂浆在泵送管内流动状态好，而从打印头打印出来后，则能够迅速进行固化。
基于以上现状，目前许多研究者着力于3D打印建筑用砂浆的研究。如，中国专利申请号为201610614696.6的申请案公开了一种可用于3D建筑打印的新型高强高韧防水砂浆材料及其制备方法，该申请案的防水砂浆材料由水泥、砂子、聚丙烯纤维、聚乙烯纤维、玄武岩纤维、HPMC纤维素、粉煤灰、减水剂、消泡剂、引气剂、有机硅防水剂、可再分散乳胶粉以及水组成。该申请案在一定程度上能够提高3D建筑打印用砂浆材料的力学强度和防水性能，但所得砂浆的流动性及固化速率可控性仍有待进一步改善。
又如，中国专利申请号为201610307917.5的申请案公开了一种3D打印砂浆及其制备方法，该申请案的3D打印砂浆主要由复配水泥70％-90％，石英砂5％-20％，石灰0.2％-2％，促凝剂1％-5％，减水剂0％-3％，消泡剂0％-3％，增稠剂0％-0.5％和纤维0.2-0.8％组成， 该申请案通过对砂浆的组分配方进行优化设计，从而可以有效提高砂浆的流动性能及施工性能，但其防水保温性能仍有待进一步提高。
发明内容
1.发明要解决的技术问题
本发明的目的在于克服现有砂浆难以同时满足3D打印建筑对防水性能、力学性能及流动、固化要求的不足，提供了一种用于3D打印建筑的防水保温砂浆及其制备方法。采用本发明的技术方案可以在保证砂浆防水保温性能的基础上，有效提高其力学性能及流动性和固化速率，从而满足3D打印建筑的需求。
2.技术方案
为达到上述目的，本发明提供的技术方案为：
其一，本发明的一种用于3D打印建筑的防水保温砂浆，其原材料包括如下质量百分比的组分：
Figure PCTCN2020082021-appb-000001
更进一步的，所述的复合水泥由低碱度硫铝酸盐水泥和超细水泥组成，其中超细水泥占复合水泥总量的30-55％。
更进一步的，所述超细水泥的平均粒径为1-4μm，其中85％以上颗粒的尺寸在4μm以下，其比表面积为1200-2200m 2/kg。
更进一步的，所述的填料采用铁尾矿渣微粉、高炉矿渣微粉或铅锌尾矿渣微粉，其粒径为3.5μm-7.5μm，所述中空玻化微珠的粒径为0.8-2.5mm，密度为50-200kg/m 3，所述膨胀蛭石粉的粒径为0.3-0.6mm，密度为60-180kg/m 3。
更进一步的，所述秸秆纤维的长度为1-1.7mm，密度为400-500kg/m 3，所述仿钢纤维的 长度为3-8mm，密度为0.7-0.85g/cm 3，初始模量为9-12GPa，断裂伸张率为32％-38％。
更进一步的，所述的复合渗透剂由乙二胺四乙酸钙钠、铸石粉和β型半水石组成，其中乙二胺四乙酸钙钠、铸石粉和β型半水石膏的质量比为(2-3):1:(2-2.5)。
更进一步的，所述的固化剂由多硫醇和氧化钙组成，多硫醇与氧化钙的质量比为4:1-6:1，且固化剂的含量为复合水泥总量的0.5-2％。
更进一步的，所述可再分散乳胶粉为醋酸乙烯酯与高级脂肪酸乙烯酯共聚胶粉；所述减水剂为聚羧酸系减水剂或脂肪族羟基磺酸盐缩合物高效减水剂。
其二，本发明的用于3D打印建筑的防水保温砂浆的制备方法，包括以下步骤：将低碱度硫铝酸盐水泥、超细水泥置于搅拌设备内搅拌3～5分钟，然后按质量配比向其中加入填料、中空玻化微珠、膨胀蛭石粉继续搅拌5～7分钟，之后再投入可再分散乳胶粉搅拌2～4分钟；继续向搅拌设备中投入复合渗透剂、消泡剂和减水剂，搅拌7～10分钟；最后投入仿钢纤维和秸秆纤维，继续搅拌9～12分钟，即得到防水保温砂浆干粉料。
其三，本发明的用于3D打印建筑的防水保温砂浆的应用，将所述防水保温砂浆直接应用于3D打印建筑，具体的，将防水保温砂浆干粉料与固化剂一起投入自动搅拌喷涂一体化设备中，搅拌4-5分钟，再加适量水搅拌后进行喷涂施工即可，其中加水量与干粉料的重量比为1:1～3，优选为1:1.6，加水搅拌至稠度为85～102mm，优选稠度为96mm。
3.有益效果
采用本发明提供的技术方案，与现有技术相比，具有如下显著效果：
(1)本发明的一种用于3D打印建筑的防水保温砂浆，通过对其原料组分及配比进行优化设计，从而一方面可以提高砂浆的防水抗渗性能，满足建筑内外墙面对防水、抗渗性能的需求，另一方面可以有效改善砂浆的流动性能，实现砂浆的快速固化及可控，进而满足对3D打印建筑的使用需求。
(2)本发明的一种用于3D打印建筑的防水保温砂浆，其复合水泥由低碱度硫铝酸盐水泥和超细水泥组成，通过低碱度硫铝酸盐水泥和超细水泥的复配，并对其复配比例进行优化设计，从而可以同时满足3D打印建筑用砂浆对强度及防渗性能的要求。同时，通过添加特定组成和配比的固化剂，通过该固化剂与超细水泥的共同和协调作用，既能够实现无机和有机成分的快速固化且可控，并保证砂浆材料前期定形的稳固性，同时还能够有效实现砂浆后期强度的快速稳定增长，保证后续打印质量。
(3)本发明的一种用于3D打印建筑的防水保温砂浆，通过向其中添加膨胀蛭石粉和中空玻化微珠，并对填料、中空玻化微珠与蛭石粉的粒度分配进行优化设计，通过三者之间的良好颗粒级配，从而可以有效提高砂浆的强度及强度稳定性。
(4)本发明的一种用于3D打印建筑的防水保温砂浆，通过向其中添加复合渗透剂，并对其组分组成和配比进行优化设计，通过乙二胺四乙酸钙钠、铸石粉和β型半水石膏的复合作用，并与复合水泥及填料一起作用，从而可以进一步提高砂浆的抗渗防水性能，使其防水效果与机械强度达到最佳配合。另外，本发明通过添加特定种类的减水剂，减水效果较好，不引气，对凝结时间基本没影响，同时与水泥的适应性很好，能与其他各种外加剂复合使用。
(5)本发明的用于3D打印建筑的防水保温砂浆的制备方法，通过对防水保温砂浆的组分、配比及具体制备工艺进行优化设计，从而可以在满足建筑用砂浆对防水保温效果要求的基础上，有效改善砂浆的流动性能，提高其固化速率，并进一步提高其力学性能，进而能够满足3D打印建筑的使用需求。
附图说明
图1为本发明各实施例及对比例中砂浆的性能对比数据。
具体实施方式
本发明通过对砂浆材料的原料组成及配比进行优化设计，从而可以有效解决现有砂浆难以同时满足3D打印建筑对防水抗渗性能、力学性能及流动、固化要求的问题。具体的，通过乙二胺四乙酸钙钠、铸石粉和β型半水石膏的复合添加，从而可以有效提高砂浆材料的双面防水、抗渗性能，同时该复合渗透剂与填料和低碱度硫铝酸盐水泥/超细水泥复配水泥的共同作用，还可以有效提高所得砂浆材料的强度，保证其防水性能与机械强度的最佳配合。另外，本发明通过向砂浆原料中添加特定种类和含量的固化剂，从而既能够实现无机和有机成分的快速固化且可控，并保证砂浆材料前期定形的稳固性，同时通过固化剂与超细水泥的共同作用还能够有效实现砂浆后期强度的快速稳定增长，保证后续打印质量。本发明的固化剂可在3～6min起固化塑形作用，其使用最低温度为-5℃，氧化钙与水反应发热起到辅助快速固化作用，同时对复合渗透剂的防水抗渗性能也有辅助加强作用。
本发明的填料采用铁尾矿渣微粉、高炉矿渣微粉或铅锌尾矿渣微粉，其粒径为3.5μm-7.5μm，中空玻化微珠的粒径为0.8-2.5mm，密度为50-200kg/m 3，膨胀蛭石粉的粒径为0.3-0.6mm，密度为60-180kg/m 3，通过填料、中空玻化微珠与膨胀蛭石粉的粒径分布优化，从而可以进一步提高砂浆的强度及强度稳定性。
为进一步了解本发明的内容，现结合具体实施例对本发明作详细描述。
实施例1
本实施例的一种用于3D打印建筑的防水保温砂浆，其原材料包括如下质量百分比的组分：
Figure PCTCN2020082021-appb-000002
Figure PCTCN2020082021-appb-000003
本实施例的复合水泥由低碱度硫铝酸盐水泥和超细水泥组成，超细水泥占复合水泥总量的30％，所述的复合渗透剂由乙二胺四乙酸钙钠、铸石粉和β型半水石膏组成，其中乙二胺四乙酸钙钠、铸石粉和β型半水石膏的质量比为2:1:2；所述的固化剂由多硫醇和氧化钙组成，多硫醇与氧化钙的质量比为4:1，且固化剂的含量为复合水泥总量的0.5％。所述可再分散乳胶粉为醋酸乙烯酯与高级脂肪酸乙烯酯共聚胶粉；所述减水剂为聚羧酸系减水剂，所述的填料采用铁尾矿渣微粉。
本实施例的用于3D打印建筑的防水保温砂浆的制备方法，包括以下步骤：将低碱度硫铝酸盐水泥、超细水泥置于搅拌设备内搅拌3分钟，然后按质量配比向其中加入填料、中空玻化微珠、膨胀蛭石粉继续搅拌7分钟，之后再投入可再分散乳胶粉搅拌4分钟；继续向搅拌设备中投入复合渗透剂、消泡剂和减水剂，搅拌7分钟；最后投入仿钢纤维和秸秆纤维，继续搅拌12分钟，即得到防水保温砂浆干粉料。
将本实施例所得防水保温砂浆直接应用于3D打印建筑，具体的，将防水保温砂浆干粉料与固化剂一起投入自动搅拌喷涂一体化设备中，搅拌4-5分钟，再加适量水搅拌后进行喷涂施工即可，其中加水量与干粉料的重量比为1:3，加水搅拌至稠度为102mm。
实施例2
本实施例的一种用于3D打印建筑的防水保温砂浆，其原材料包括如下质量百分比的组分：
Figure PCTCN2020082021-appb-000004
Figure PCTCN2020082021-appb-000005
本实施例的复合水泥由低碱度硫铝酸盐水泥和超细水泥组成，超细水泥占复合水泥总量的43％，所述的复合渗透剂由乙二胺四乙酸钙钠、铸石粉和β型半水石膏组成，其中乙二胺四乙酸钙钠、铸石粉和β型半水石膏的质量比为3:1:2.5；所述的固化剂由多硫醇和氧化钙组成，多硫醇与氧化钙的质量比为5:1，且固化剂的含量为复合水泥总量的1.3％。所述醋酸乙烯酯与高级脂肪酸乙烯酯共聚胶粉，所述减水剂为脂肪族羟基磺酸盐缩合物高效减水剂，所述的填料采用高炉矿渣微粉。
本实施例的用于3D打印建筑的防水保温砂浆的制备方法，包括以下步骤：将低碱度硫铝酸盐水泥、超细水泥置于搅拌设备内搅拌5分钟，然后按质量配比向其中加入填料、中空玻化微珠、膨胀蛭石粉继续搅拌5分钟，之后再投入可再分散乳胶粉搅拌2分钟；继续向搅拌设备中投入复合渗透剂、消泡剂和减水剂，搅拌10分钟；最后投入仿钢纤维和秸秆纤维，继续搅拌9分钟，即得到防水保温砂浆干粉料。
将本实施例所得防水保温砂浆直接应用于3D打印建筑，具体的，将防水保温砂浆干粉料与固化剂一起投入自动搅拌喷涂一体化设备中，搅拌4-5分钟，再加适量水搅拌后进行喷涂施工即可，其中加水量与干粉料的重量比为1:1，加水搅拌至稠度为85mm。
实施例3
本实施例的一种用于3D打印建筑的防水保温砂浆，其原材料包括如下质量百分比的组分：
Figure PCTCN2020082021-appb-000006
Figure PCTCN2020082021-appb-000007
本实施例的复合水泥由低碱度硫铝酸盐水泥和超细水泥组成，超细水泥占复合水泥总量的55％，所述的复合渗透剂由乙二胺四乙酸钙钠、铸石粉和β型半水石膏组成，其中乙二胺四乙酸钙钠、铸石粉和β型半水石膏的质量比为2.5:1:2.2；所述的固化剂由多硫醇和氧化钙组成，多硫醇与氧化钙的质量比为6:1，且固化剂的含量为复合水泥总量的2％。所述可再分散乳胶粉为醋酸乙烯酯与高级脂肪酸乙烯酯共聚胶粉，所述减水剂为聚羧酸系减水剂，所述的填料采用铅锌尾矿渣微粉。
本实施例的用于3D打印建筑的防水保温砂浆的制备方法，包括以下步骤：将低碱度硫铝酸盐水泥、超细水泥置于搅拌设备内搅拌4分钟，然后按质量配比向其中加入填料、中空玻化微珠、膨胀蛭石粉继续搅拌6分钟，之后再投入可再分散乳胶粉搅拌3分钟；继续向搅拌设备中投入复合渗透剂、消泡剂和减水剂，搅拌8分钟；最后投入仿钢纤维和秸秆纤维，继续搅拌10分钟，即得到防水保温砂浆干粉料。
将本实施例所得防水保温砂浆直接应用于3D打印建筑，具体的，将防水保温砂浆干粉料与固化剂一起投入自动搅拌喷涂一体化设备中，搅拌4-5分钟，再加适量水搅拌后进行喷涂施工即可，其中加水量与干粉料的重量比为1:1.6，加水搅拌至稠度为96mm。
对比例1：
本对比例的砂浆中各组分的重量百分数如下：
Figure PCTCN2020082021-appb-000008
上述复合渗透剂包括氢氧化钙、羟乙二胺四醋酸和粉状速溶氟硅酸钠，其重量百分比分别为1.2％、1.4％和0.6％，填料和固化剂的组成与实施例1相同。
对比例2：
本对比例各组分的重量百分数为：
Figure PCTCN2020082021-appb-000009
本对比例的填料、复合渗透剂、消泡剂及减水剂的种类均同实施例2。
对比例3：
本对比例各组分的重量百分数为：
Figure PCTCN2020082021-appb-000010
本对比例的填料、固化剂、消泡剂及减水剂的种类均同实施例3。
实施例1-3及对比例1-3中砂浆的性能对比数据如图1所示，由图1可以看出，通过采用本发明的砂浆配方，可以同时满足3D建筑打印对防水抗渗性能、机械性能和固化速度的 要求。

Claims (10)

  1. 一种用于3D打印建筑的防水保温砂浆，其特征在于，其原材料包括如下质量百分比的组分：
    Figure PCTCN2020082021-appb-100001
  2. 根据权利要求1所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述的复合水泥由低碱度硫铝酸盐水泥和超细水泥组成，其中超细水泥占复合水泥总量的30-55％。
  3. 根据权利要求1所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述超细水泥的平均粒径为1-4μm，其中85％以上颗粒的尺寸在4μm以下，其比表面积为1200-2200m 2/kg。
  4. 根据权利要求3所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述的填料采用铁尾矿渣微粉、高炉矿渣微粉或铅锌尾矿渣微粉，其粒径为3.5μm-7.5μm，所述中空玻化微珠的粒径为0.8-2.5mm，密度为50-200kg/m 3，所述膨胀蛭石粉的粒径为0.3-0.6mm，密度为60-180kg/m 3。
  5. 根据权利要求1-4中任一项所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述秸秆纤维的长度为1-1.7mm，密度为400-500kg/m 3，所述仿钢纤维的长度为3-8mm，密度为0.7-0.85g/cm 3，初始模量为9-12GPa，断裂伸张率为32％-38％。
  6. 根据权利要求1-4中任一项所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述的复合渗透剂由乙二胺四乙酸钙钠、铸石粉和β型半水石组成，其中乙二胺四乙酸钙钠、铸石粉和β型半水石膏的质量比为(2-3):1:(2-2.5)。
  7. 根据权利要求6所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述的固化剂由多硫醇和氧化钙组成，多硫醇与氧化钙的质量比为4:1-6:1，且固化剂的含量为复合水泥总量的0.5-2％。
  8. 根据权利要求6所述的一种用于3D打印建筑的防水保温砂浆，其特征在于：所述可再分散乳胶粉为醋酸乙烯酯与高级脂肪酸乙烯酯共聚胶粉；所述减水剂为聚羧酸系减水剂或脂肪族羟基磺酸盐缩合物高效减水剂。
  9. 一种如权利要求1-9中任一项所述的用于3D打印建筑的防水保温砂浆的制备方法，其特征在于，包括以下步骤：将低碱度硫铝酸盐水泥、超细水泥置于搅拌设备内搅拌3～5分钟，然后按质量配比向其中加入填料、中空玻化微珠、膨胀蛭石粉继续搅拌5～7分钟，之后再投入可再分散乳胶粉搅拌2～4分钟；继续向搅拌设备中投入复合渗透剂、消泡剂和减水剂，搅拌7～10分钟；最后投入仿钢纤维和秸秆纤维，继续搅拌9～12分钟，即得到防水保温砂浆干粉料。
  10. 一种如权利要求1-9中任一项所述的用于3D打印建筑的防水保温砂浆的应用，其特征在于：将所述防水保温砂浆直接应用于3D打印建筑，具体的，将防水保温砂浆干粉料与固化剂一起投入自动搅拌喷涂一体化设备中，搅拌4-5分钟，再加适量水搅拌后进行喷涂施工即可，其中加水量与干粉料的重量比为1:1～3，优选为1:1.6，加水搅拌至稠度为85～102，优选稠度为96。
PCT/CN2020/082021 2019-05-13 2020-03-30 一种用于3d打印建筑的防水保温砂浆及其制备方法和应用 WO2020228432A1 (zh)

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CN113121175A (zh) * 2021-05-11 2021-07-16 河南省宜居建材科技有限公司 一种无机活性保温砂浆
CN115417630A (zh) * 2022-09-16 2022-12-02 湖南斯多孚节能科技有限公司 一种绿色环保型改性玻化微珠轻质预拌砂浆制备及其应用
CN115417630B (zh) * 2022-09-16 2024-03-22 湖南斯多孚节能科技有限公司 一种绿色环保型改性玻化微珠轻质预拌砂浆制备及其应用
CN116102334A (zh) * 2022-11-30 2023-05-12 燕山大学 一种基于碱渣的3d打印碱激发纤维混凝土及其制备方法和打印方法
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CN116177933A (zh) * 2022-12-29 2023-05-30 四川昊龙高科轨道交通新材料科技股份有限公司 一种防冲撞混凝土盖板及其制备工艺
CN116283223A (zh) * 2023-03-23 2023-06-23 东北大学 一种基于铁尾矿的陶瓷3d打印材料及制备方法
CN116283223B (zh) * 2023-03-23 2024-04-09 东北大学 一种基于铁尾矿的陶瓷3d打印材料及制备方法

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