WO2021109991A1

WO2021109991A1 - Concrete for inducing attachment of marine sessile organisms and preparation method therefor

Info

Publication number: WO2021109991A1
Application number: PCT/CN2020/133100
Authority: WO
Inventors: 吕建福; 马小兵; 汪明军
Original assignee: 哈尔滨工程大学
Priority date: 2019-12-02
Filing date: 2020-12-01
Publication date: 2021-06-10

Abstract

Disclosed is technology for inducing the attachment of marine sessile organisms, and in particular concrete for inducing the adhesion of marine sessile organisms and a preparation method therefor. The concrete has the characteristics of having a small doping amount of an inducer and there being no influence on the strength and permeability of the concrete, and achieves the aim of inducing the attachment and metamorphosis of sessile organisms and promoting long-term growth of sessile organisms, and the concrete may be applied to the fields of corrosion prevention of reinforced concrete structures in tidal range areas and ecological restoration of marine environments.

Description

诱导海洋固着生物附着的混凝土及制备方法Concrete for inducing adhesion of marine fixed organisms and preparation method

本申请要求于2019年12月2日提交中国专利局、申请号为201911210606.7，发明名称为“一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土及制备方法”的中国专利申请的优先权，要求2019年12月2日提交中国专利局、申请号为201911210489.4，发明名称为“一种诱导海洋固着生物附着的绿色混凝土及制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed with the Chinese Patent Office on December 2, 2019, the application number is 201911210606.7, and the invention title is "A dark Portland cement concrete that induces the attachment of marine sessile organisms and its preparation method". , Requires the priority of a Chinese patent application filed with the Chinese Patent Office on December 2, 2019, with application number 201911210489.4, and the title of the invention “a green concrete for inducing the attachment of marine fixed organisms and its preparation method”, the entire content of which is incorporated by reference In this application.

技术领域Technical field

本发明涉及一种诱导海洋固着生物附着的技术，尤其涉及一种诱导海洋固着生物附着的混凝土及制备方法，属于海洋固着生物与混凝土交叉领域。The invention relates to a technology for inducing the attachment of marine sessile organisms, in particular to a concrete for inducing the attachment of marine sessile organisms and a preparation method, belonging to the cross field of marine sessile organisms and concrete.

背景技术Background technique

钢筋混凝土广泛应用于海洋基础设施建设中，如海港码头、跨海大桥、海洋平台和海底隧道等。然而，因氯离子侵蚀导致的钢筋锈蚀问题极大地缩短了钢筋混凝土结构的服役寿命，给社会带来巨大的经济负担。迄今为止，对于海洋环境下的钢筋混凝土工程，具有代表性的防腐蚀技术主要包括高性能混凝土、表面涂层、FRP筋、钢筋阻锈剂和电化学防护技术等。这些防腐蚀技术都存在一些缺点或不足，如施工难度大、材料易老化耐久性不足、长期不可预见性、成本高等中的一个或多个。此外，目前的防腐蚀技术大多数是针对于浪溅区，而对于潮差区的防腐蚀，存在措施少、成本高以及防腐蚀效果差的问题。Reinforced concrete is widely used in the construction of marine infrastructure, such as harbor terminals, cross-sea bridges, ocean platforms, and subsea tunnels. However, the corrosion of steel bars caused by chloride ion erosion greatly shortens the service life of reinforced concrete structures and brings a huge economic burden to the society. So far, for reinforced concrete projects in the marine environment, representative anti-corrosion technologies mainly include high-performance concrete, surface coatings, FRP bars, steel bar rust inhibitors, and electrochemical protection technologies. These anti-corrosion technologies all have some shortcomings or deficiencies, such as one or more of the difficulty of construction, the lack of durability of materials easily aging, long-term unpredictability, and high cost. In addition, most of the current anti-corrosion technologies are aimed at the splash area, and for the anti-corrosion in the tidal range, there are problems of fewer measures, high costs, and poor anti-corrosion effects.

发明内容Summary of the invention

本发明的目的是为了解决目前采用单掺钙质材料的混凝土底质，存在掺量过大，混凝土耐久性严重不良，以及诱导牡蛎幼虫附着效率低的问题而提供一种诱导固着生物快速、致密地附着且高耐久的混凝土The purpose of the present invention is to solve the problems of the existing concrete substrates with single-doped calcium materials, which are excessively mixed, the durability of concrete is seriously poor, and the efficiency of inducing oyster larvae is low, and to provide a rapid and dense induction of sessile organisms. Ground-attached and highly durable concrete

本发明的目的是这样实现的：本发明通过使用低碱度的掺矿物掺合料的硅酸盐水泥，并在混凝土中添加深色颜料、生物钙粉并控制混凝土渗透性的方法，使混凝土具有高诱导牡蛎幼虫附着、***的能力。The purpose of the present invention is achieved as follows: The present invention uses low alkalinity Portland cement mixed with mineral admixtures, and adds dark pigments and biological calcium powder to the concrete and controls the permeability of the concrete to make the concrete It has a high ability to induce attachment and metamorphosis of oyster larvae.

本发明还包括这样一些结构特征：The invention also includes such structural features:

其材料1组分为：硅酸盐水泥、矿物掺合料、碎石、砂、水、深色颜料、生物钙粉和超塑化剂制成重量配比依次为：8.5％～16.0％、3.5％～11.0％、39.4％～49.8％、24.9％～37.3％、6.2％～8.7％、0.2％～1.7％、0.2～1.7％和0.02％～0.1％。The first component of the material is: Portland cement, mineral admixtures, crushed stone, sand, water, dark pigments, bio-calcium powder and superplasticizer in the weight ratio: 8.5% to 16.0%, 3.5% to 11.0%, 39.4% to 49.8%, 24.9% to 37.3%, 6.2% to 8.7%, 0.2% to 1.7%, 0.2 to 1.7% and 0.02% to 0.1%.

优选的，所述的深色颜料为：氧化铁黑、苯胺黑、炭黑、硫化锑、氧化铁红、有机颜料红中的一种或两种，根据对混凝土的性能影响程度，进行这些颜料的改性，采用透明树脂、有机硅、二甲硅氧烷、超疏水材料中的一种进行改性处理。Preferably, the dark pigment is one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red, and organic pigment red. These pigments are used according to the degree of influence on the performance of concrete. For the modification, use one of transparent resin, organic silicon, dimethicone, and super-hydrophobic material for modification treatment.

优选的，所述的生物钙粉为牛骨粉和生物碳酸钙粉包括牡蛎壳粉、鱼骨粉、鸡蛋壳粉、珊瑚粉中的一种或几种复合，其细度为100目～1000目。Preferably, the biological calcium powder is beef bone powder and biological calcium carbonate powder, including one or more of oyster shell powder, fish bone powder, egg shell powder, and coral powder, with a fineness of 100 mesh to 1000 mesh.

优选的，所述的生物钙粉改性方法：对100目到500目间的牡蛎壳粉、鸡蛋壳粉、珊瑚粉、鱼骨粉采用以下酸进行处理，包括乙酸、醋酸、硅酸、亚硫酸中的一种或两种；以及对100目到500目牛骨粉采用以下酸进行处理，包括稀释的磷酸、硫酸、盐酸和硝酸中的一种或两种。Preferably, the method for modifying biological calcium powder: treat oyster shell powder, egg shell powder, coral powder, and fish bone powder between 100 mesh and 500 mesh with the following acids, including acetic acid, acetic acid, silicic acid, and sulfurous acid One or two of them; and the use of the following acids for treatment of 100 mesh to 500 mesh beef bone meal, including one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

优选的，所述的硅酸盐水泥为普通硅酸盐水泥，强度等级＞32.5，所述的矿物掺合料包括硅灰、矿渣粉和粉煤灰中的一种或多种组合。Preferably, the Portland cement is ordinary Portland cement with a strength grade> 32.5, and the mineral admixture includes one or more combinations of silica fume, slag powder and fly ash.

优选的，所述的砂为河砂、机制砂或者淡化海砂中的一种或几种，且级配良好。Preferably, the sand is one or more of river sand, machine-made sand or desalinated sea sand, and has a good gradation.

一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土的制备方法，包括如下步骤：A preparation method of dark Portland cement concrete for inducing the attachment of marine sessile organisms, including the following steps:

S1：精确称量硅酸盐水泥、矿物掺合料、碎石、砂、水、深色颜料、生物钙粉和超塑化剂；S1: Accurately weigh Portland cement, mineral admixtures, gravel, sand, water, dark pigments, biological calcium powder and superplasticizer;

S2：先将碎石和砂放入混凝土搅拌机中搅拌0.5～1分钟；然后加入硅酸盐水泥、矿物掺合料、生物钙粉、深色颜料，再继续搅拌0.5～1分钟；然后加入水和超塑化剂搅拌2～6分钟；搅拌均匀后，进行浇筑、振捣，随后进行标准养护28d或根据实际情况进行养护，即可制得诱导效果良好的海洋固着生物附着的深色硅酸盐水泥混凝土。S2: Put the gravel and sand into the concrete mixer and mix for 0.5 to 1 minute; then add Portland cement, mineral admixtures, biological calcium powder, and dark pigments, and continue to mix for 0.5 to 1 minute; then add water Stir it with superplasticizer for 2-6 minutes; after stirring evenly, pour, vibrate, and then carry out standard curing for 28 days or curing according to the actual situation, you can prepare dark silicic acid with good inducing effect for marine sessile organism adhesion Salt cement concrete.

其材料2组分为：深色颜料、胶凝材料、碎石、砂、水和超塑化剂，其中，深色颜料、胶凝材料、碎石、砂、水和超塑化剂粉重量配比依次为：0.2％～1.7％、12.5％～22.0％、39.4％～49.8％、24.9％～37.3％、6.2％～8.7％、0.02％～0.1％。The two components of the material are: dark pigment, gelling material, crushed stone, sand, water and superplasticizer, among which, the weight of dark pigment, gelling material, crushed stone, sand, water and superplasticizer powder The proportions are: 0.2% to 1.7%, 12.5% to 22.0%, 39.4% to 49.8%, 24.9% to 37.3%, 6.2% to 8.7%, 0.02% to 0.1%.

其材料3组分为：生物钙粉、胶凝材料、碎石、砂、水和超塑化剂，其中，生物钙粉、胶凝材料、碎石、砂、水和超塑化剂重量配比依次为：0.2％～1.7％、12.5％～22.0％、39.4％～49.8％、24.9％～37.3％、6.2％～8.7％、0.02％～0.1％。The three components of the material are: biological calcium powder, cementitious material, crushed stone, sand, water and superplasticizer. Among them, biological calcium powder, cementitious material, crushed stone, sand, water and superplasticizer are weighted The ratios are: 0.2% to 1.7%, 12.5% to 22.0%, 39.4% to 49.8%, 24.9% to 37.3%, 6.2% to 8.7%, 0.02% to 0.1%.

本发明的目的是为了解决目前采用单掺钙质材料的混凝土底质，存在掺量过大，混凝土耐久性严重不良，以及诱导牡蛎幼虫附着效率低的问题而提供一种诱导固着生物快速、致密地附着且高耐久的混凝土。The purpose of the present invention is to solve the problems of the existing concrete substrates with single-doped calcium materials, which are excessively mixed, the durability of concrete is seriously poor, and the efficiency of inducing oyster larvae is low, and to provide a rapid and dense induction of sessile organisms. Ground-attached and highly durable concrete.

本发明的目的是这样实现的：本发明通过使用低碱度水泥，并在混凝土中添加深色颜料、生物钙粉、改性的碳酸(氢)盐并控制混凝土渗透性的方法，使混凝土具有高诱导牡蛎幼虫附着、***的能力，同时掺加大量的贝壳砂，既实现了废弃物的利用，又保证了混凝土的高耐久性，且对海洋环境无污染。The purpose of the present invention is achieved as follows: The present invention uses low-alkalinity cement, and adds dark pigments, biological calcium powder, modified bicarbonate (bicarbonate) salt to the concrete and controls the permeability of the concrete, so that the concrete has Highly inducing the attachment and metamorphosis of oyster larvae, and adding a large amount of shell sand at the same time, it not only realizes the utilization of waste, but also ensures the high durability of concrete without pollution to the marine environment.

其材料1组分包括：胶凝材料、碎石、砂、水、深色颜料、生物钙粉、生物碳酸钙颗粒、碳酸(氢)盐和超塑化剂，重量配比依次为：13.3％～22.8％、39.4％～49.8％、0％～24.6％、6.2％～8.7％、0.2％～1.7％、0.2～1.7％、8.0％～33.5％、0.2～1.7％和0.02％～0.1％。The 1 component of its material includes: gelling material, gravel, sand, water, dark pigment, biological calcium powder, biological calcium carbonate particles, (bicarbonate) salt and superplasticizer, the weight ratio is: 13.3% ～22.8%, 39.4%～49.8%, 0%～24.6%, 6.2%～8.7%, 0.2%～1.7%, 0.2～1.7%, 8.0%～33.5%, 0.2～1.7% and 0.02%～0.1%.

优选的，所述的深色颜料为氧化铁黑、苯胺黑、炭黑、硫化锑、氧化铁红、有机颜料红中的一种或两种。根据对混凝土的性能影响程度，进行这些颜料的改性，采用透明树脂、有机硅、二甲硅氧烷、超疏水材料中的一种进行改性处理。Preferably, the dark pigment is one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red, and organic pigment red. According to the degree of influence on the performance of concrete, these pigments are modified, and one of transparent resin, silicone, dimethylsiloxane, and superhydrophobic materials is used for modification.

优选的，所述的生物钙粉为牛骨粉与生物碳酸钙粉包括牡蛎壳粉、鱼骨粉、鸡蛋壳粉、珊瑚粉中的一种或几种复合，其细度为100目～1000目。Preferably, the biological calcium powder is a combination of beef bone powder and biological calcium carbonate powder, including one or more of oyster shell powder, fish bone powder, egg shell powder, and coral powder, with a fineness of 100 mesh to 1000 mesh.

优选的，所述的生物钙粉：对100目到500目间的鸡蛋壳粉、珊瑚粉、牡蛎壳粉、鱼骨粉采用以下酸进行处理，包括乙酸、醋酸、硅酸、亚硫酸中的一种或两种；以及对100目到500目牛骨粉采用以下酸处理，包括稀释的磷酸、硫酸、盐酸和硝酸中的一种或两种。Preferably, the biological calcium powder: the egg shell powder, coral powder, oyster shell powder, and fish bone powder between 100 mesh and 500 mesh are treated with the following acids, including one of acetic acid, acetic acid, silicic acid, and sulfurous acid. One or two kinds; and the following acid treatment is used for 100 mesh to 500 mesh cattle bone meal, including one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

优选的，所述的胶凝材料为硫铝酸盐水泥、碱激发胶凝材料中的一种；硫铝酸盐水泥，包括快硬硫铝酸盐水泥、高强硫铝酸盐水泥、膨胀硫铝酸盐水泥中的一种或两种；碱激发胶凝材料为碱激发矿渣、碱激发矿渣+粉煤灰。Preferably, the cementing material is one of sulphoaluminate cement and alkali-activated cementing material; sulphoaluminate cement includes fast hardening sulphoaluminate cement, high-strength sulphoaluminate cement, expanded sulfur One or two of aluminate cement; alkali-activated cementitious materials are alkali-activated slag, alkali-activated slag + fly ash.

优选的，所述的改性的碳酸(氢)盐为碳酸钠、碳酸钾，碳酸氢钙、碳酸氢钠、碳酸氢钾中的一种或几种，采用硅藻土作为载体，与这些无机盐复合后实现相应离子的缓释及减少或者消除对混凝土性能的不良影响。Preferably, the modified carbonate (bicarbonate) salt is one or more of sodium carbonate, potassium carbonate, calcium bicarbonate, sodium bicarbonate, and potassium bicarbonate, using diatomaceous earth as a carrier, and these inorganic After the salt is compounded, the slow release of corresponding ions can be realized and the adverse effects on the performance of concrete can be reduced or eliminated.

优选的，所述的生物碳酸钙颗粒为，牡蛎壳、珊瑚其中的一种或两种，其颗粒的尺寸为0.16～5.0mm，并符合II区中砂的级配，用来取代混凝土配合比中的砂。Preferably, the biological calcium carbonate particles are one or two of oyster shells and corals, and the size of the particles is 0.16～5.0mm, and conforms to the gradation of sand in Zone II, and is used to replace concrete mix ratio In the sand.

优选的，所述的砂为河砂、机制砂(母岩为玄武岩或花岗岩的一种)或者淡化海砂中的一种或几种，且级配良好。Preferably, the sand is one or more of river sand, machine-made sand (the parent rock is one of basalt or granite), or desalinated sea sand, and has a good gradation.

一种诱导海洋固着生物附着的绿色混凝土的制备方法，包括如下步骤：A method for preparing green concrete for inducing the attachment of marine sessile organisms includes the following steps:

S1：精确称量胶凝材料、碎石、砂、水、深色颜料、生物钙粉、生物碳酸钙颗粒、改性的碳酸(氢)盐和超塑化剂；S1: Accurately weigh cementitious materials, gravel, sand, water, dark pigments, biological calcium powder, biological calcium carbonate particles, modified bicarbonate (bicarbonate) salts and superplasticizers;

S2：先将碎石、砂、生物碳酸钙颗粒放入混凝土搅拌机中搅拌0.5～1分钟；然后加入胶凝材料、生物钙粉、深色颜料及改性的碳酸(氢)盐，再继续搅拌0.5～1分钟；然后加入水和超塑化剂搅拌2～6分钟；搅拌均匀后，进行浇筑、振捣，进行标准养护28d或根据实际情况进行养护，即可制得诱导效果良好的海洋固着生物附着的绿色混凝土。S2: Put the gravel, sand and biological calcium carbonate particles into the concrete mixer and mix for 0.5 to 1 minute; then add the cementitious material, biological calcium powder, dark pigment and modified bicarbonate (bicarbonate) salt, and then continue to mix 0.5 to 1 minute; then add water and superplasticizer and stir for 2 to 6 minutes; after mixing evenly, pour, vibrate, and carry out standard curing for 28 days or curing according to the actual situation, you can obtain a sea fixation with good induction effect Biologically attached green concrete.

其材料2组分为：深色颜料、胶凝材料、碎石、砂、水和超塑化剂，其中，深色颜料、胶凝材料、碎石、砂、水和超塑化剂重量配比依次为：0.2％～1.7％、13.3％～22.8％、39.4％～49.8％、8.0％～24.6％、6.2％～8.7％和0.02％～0.1％。The two components of the material are: dark pigment, gelling material, crushed stone, sand, water and superplasticizer, among which the dark pigment, gelling material, crushed stone, sand, water and superplasticizer are weighted The ratios are: 0.2% to 1.7%, 13.3% to 22.8%, 39.4% to 49.8%, 8.0% to 24.6%, 6.2% to 8.7%, and 0.02% to 0.1%.

其材料3组分为：生物钙粉、胶凝材料、碎石、砂、水和超塑化剂，其中，生物钙粉、胶凝材料、碎石、砂、水和超塑化剂重量配比依次为：0.2％～1.7％、13.3％～22.8％、39.4％～49.8％、8.0％～24.6％、6.2％～8.7％和0.02％～0.1％。The three components of the material are: biological calcium powder, cementitious material, crushed stone, sand, water and superplasticizer. Among them, biological calcium powder, cementitious material, crushed stone, sand, water and superplasticizer are weighted The ratios are: 0.2% to 1.7%, 13.3% to 22.8%, 39.4% to 49.8%, 8.0% to 24.6%, 6.2% to 8.7%, and 0.02% to 0.1%.

其材料4组分为：深色颜料、胶凝材料、碎石、砂、水、碳酸盐或碳酸氢盐和超塑化剂，其中，深色颜料、胶凝材料、碎石、砂、水、碳酸盐或碳酸氢盐和超塑化剂重量配比依次为：0.2％～1.7％、13.3％～22.8％、39.4％～49.8％、8.0％～24.6％、6.2％～8.7％、0.2～1.7％和0.02％～0.1％。The four components of the material are: dark pigments, gelling materials, gravel, sand, water, carbonate or bicarbonate and superplasticizers, among which, dark pigments, gelling materials, gravel, sand, The weight ratio of water, carbonate or bicarbonate and superplasticizer is 0.2%～1.7%, 13.3%～22.8%, 39.4%～49.8%, 8.0%～24.6%, 6.2%～8.7%, 0.2～1.7% and 0.02%～0.1%.

本发明的有益效果在于：The beneficial effects of the present invention are:

混凝土的强度和渗透性是混凝土最主要的两个性能。而在基准混凝土中掺加不同的诱导剂，都会对混凝土性能产生影响，因此，在考虑掺加不同物质促进牡蛎幼虫附着、***及后期生长时，首先一定要从整体控制其对混凝土的强度和渗透性不产生大的影响，然后再根据各种原材料的配伍性去选择原材料，当原材料性能不能满足实际要求时，则通过对原材料的改性后再加入，从而达到我们期望的功能。The strength and permeability of concrete are the two most important properties of concrete. The addition of different inducers to the benchmark concrete will have an impact on the performance of the concrete. Therefore, when considering the addition of different substances to promote the attachment, metamorphosis and later growth of the oyster larvae, the overall strength and strength of the concrete must be controlled first. The permeability does not have a big impact, and then select the raw materials according to the compatibility of various raw materials. When the performance of the raw materials cannot meet the actual requirements, the raw materials are modified and then added to achieve the desired function.

本发明通过控制采用稀酸改性和复合粉磨技术，充分发挥牛骨粉的诱导能力，大幅度降低牛骨粉掺量，并进行防腐蚀处理及改性，实现了以牛骨粉为主的复合诱导剂，其掺量小，几乎不影响混凝土强度和渗透性，同时具有很强的牡蛎幼虫附着能力，且解决了混凝土的发霉问题。相对于不掺加诱导剂的混凝土，掺加诱导剂的混凝土牡蛎幼虫附着个数明显增加。本发明采用低碱度的硫铝酸盐水泥的复合，调控水泥混凝土的碱度，为牡蛎幼虫附着提供适宜的pH值。此外，海洋植物和牡蛎、藤壶等固着生物耐碱能力不同，且在附着期及后期需要的环境不同，如藤壶和牡蛎的附着、***及后期生长都需要大量的钙离子。以及由于硫铝酸盐水泥的碱度低，并且快硬硫铝酸盐水泥、高强硫铝酸盐水泥、膨胀硫铝酸盐的碱度不同，可以根据实际所需的碱度进行复合掺加，可以给牡蛎和藤壶幼虫在其表面附着提供适宜的碱度。同时硫铝酸盐水泥具有早强、高强的特点，可以实现工程的快速建造，同时具有高的抗渗性能和耐腐蚀性，特别是具有高的抗硫酸盐腐蚀的性能，在海洋工程以及需快速修补工程中具有显著的优势。By controlling the use of dilute acid modification and composite grinding technology, the present invention gives full play to the inducing ability of bovine bone powder, greatly reduces the amount of bovine bone powder, and carries out anti-corrosion treatment and modification, and realizes the compound induction based on bovine bone powder. It has a small content and hardly affects the strength and permeability of concrete. At the same time, it has strong adhesion of oyster larvae, and solves the problem of mildew in concrete. Compared with the concrete without the inducer, the number of oyster larvae on the concrete with the inducer increased significantly. The invention adopts the compound of low alkalinity sulphoaluminate cement to regulate the alkalinity of cement concrete and provide suitable pH value for the attachment of oyster larvae. In addition, marine plants and oysters, barnacles and other sessile organisms have different alkali resistance capabilities, and require different environments during the attachment period and later period. For example, barnacles and oysters require a large amount of calcium ions for attachment, metamorphosis, and late growth. And because the alkalinity of sulphoaluminate cement is low, and the alkalinity of fast hardening sulphoaluminate cement, high-strength sulphoaluminate cement, and expanded sulphoaluminate cement is different, it can be compounded according to the actual alkalinity required. , Can provide suitable alkalinity for oysters and barnacle larvae to attach on their surface. At the same time, sulfoaluminate cement has the characteristics of early strength and high strength, which can realize the rapid construction of the project, and at the same time has high impermeability and corrosion resistance, especially high sulfate corrosion resistance. It is used in marine engineering and demand It has significant advantages in rapid repair engineering.

附图说明Description of the drawings

图1掺加10％牛骨粉的不同配合比的混凝土表面发霉情况。Fig. 1 Mold on the surface of concrete mixed with 10% bovine bone powder in different mixing ratios.

图2掺加细度大于200目、改性的10％牛骨粉的不同配合比。Figure 2 Mixing ratios of modified 10% bovine bone meal with a fineness greater than 200 meshes.

图3实海附着实验210d示意图。Figure 3 Schematic diagram of the actual sea attachment experiment 210d.

图4实海附着实验300d示意图。Figure 4 300d schematic diagram of the actual sea attachment experiment.

具体实施方式Detailed ways

下面通过实施例对本发明进行详细说明，这些实施例仅用来说明本发明，并不限制本发明的范围。实施例1～16实施方法相同，混凝土配合比如下：The present invention will be described in detail below through examples. These examples are only used to illustrate the present invention and do not limit the scope of the present invention. The implementation methods of Examples 1-16 are the same, and the concrete mixing ratio is as follows:

实施例1：普通硅酸盐水泥混凝土配合比是指普通硅酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：17.1％、46.67％、29.0％、7.2％、0.03％。Example 1: The mixing ratio of ordinary Portland cement concrete refers to the weight ratio of ordinary Portland cement, crushed stone, sand, water and polycarboxylate water-reducing agent powder in order: 17.1%, 46.67%, 29.0%, 7.2 %, 0.03%.

其中所述的碎石的母岩为玄武岩和辉绿岩中一种，其最大粒径不超过50mm，且级配良好；所述的砂为河砂、机制砂(母岩为花岗岩、玄武岩中的一种)或者淡化海砂中的一种或几种，且级配良好。所述的水应符合混凝土用水标准(JGJ63-2006)，Cl ^-含量＜1000mg/L，PH值＞4.5，对水泥初凝时间差及终凝时间、强度及渗透性影响小。且实施例1～16中所选以上材料相同。 The parent rock of the gravel is one of basalt and diabase, and its maximum particle size is no more than 50mm, and the gradation is good; the sand is river sand, machine-made sand (the parent rock is granite, basalt One) or desalinated one or more of the sea sand, and the gradation is good. The said water should comply with the water standard for concrete (JGJ63-2006), Cl ^- content <1000mg/L, PH value>4.5, and has little effect on the initial setting time difference and final setting time, strength and permeability of cement. And the above materials selected in Examples 1-16 are the same.

实施例2：基准混凝土配合比：普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：10.26％、0.86％、5.98％、46.67％、29.0％、7.2％、0.03％。Example 2: Benchmark concrete mixing ratio: ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water reducer powder in weight ratio: 10.26%, 0.86%, 5.98% , 46.67%, 29.0%, 7.2%, 0.03%.

以上实例表明，将高炉矿渣粉及硅灰掺入混凝土中，不但可以填充水泥等颗粒间的空隙，还可以发生火山灰反应，进而改善过渡区界面微结构，这样既保证了混凝土的基本强度，又降低了混凝土自身碱度以及渗透性。在降低混凝土与其接触海水间碱度差效果的同时，其低渗透性也可以控制碱的释放速率，最后使牡蛎幼虫更易附着于混凝土表面。The above examples show that mixing blast furnace slag powder and silica fume into concrete can not only fill the voids between cement and other particles, but also cause pozzolanic reaction to improve the interface microstructure of the transition zone, which not only ensures the basic strength of concrete, but also Reduce the alkalinity and permeability of concrete itself. While reducing the effect of the difference in alkalinity between concrete and its contact with seawater, its low permeability can also control the rate of alkali release, and finally make it easier for oyster larvae to attach to the surface of the concrete.

实施例3：未改性深色颜料、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、10.26％、0.79％、5.54％、46.67％、29.0％、7.2％、0.03％。Example 3: The weight ratio of unmodified dark pigment, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例4：未改性深色颜料、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、10.26％、0.75％、5.23％、46.67％、29.0％、7.2％、0.03％。Example 4: The weight ratio of unmodified dark pigment, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例5：未改性深色颜料、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、10.26％、0.68％、4.79％、46.67％、29.0％、7.2％、0.03％。Example 5: The weight ratio of unmodified dark pigment, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water reducing agent powder is 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例6：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、10.26％、0.79％、5.54％、46.67％、29.0％、7.2％、0.03％。Example 6: Modified dark pigment (iron oxide black: aniline black mixture mass ratio = 1:1), ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid for water reduction The weight ratio of the powder is 0.51%, 10.26%, 0.79%, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例7：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、10.26％、0.75％、5.23％、46.67％、29.0％、7.2％、0.03％。Example 7: Modified dark pigment (iron oxide black: aniline black mixture mass ratio = 1:1), ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid for water reduction The weight ratio of the agent powder is: 0.86%, 10.26%, 0.75%, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例8：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、10.26％、0.68％、4.79％、46.67％、29.0％、7.2％、0.03％。Example 8: Modified dark pigment (mass ratio of iron oxide black: aniline black mixture = 1:1), ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid to reduce water The weight ratio of the agent powder is: 1.37%, 10.26%, 0.68%, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

其中改性深色颜料采用196透明树脂，掺加3％的固化剂和1.5％促进剂同颜料混合，且颜料与树脂的体积比为：1:0.2；常温固化4h，60℃固化4h，然后敲碎，用振动磨研磨，细度大于400目即可。Among them, the modified dark pigment uses 196 transparent resin, mixed with 3% curing agent and 1.5% accelerator, and the volume ratio of pigment to resin is 1:0.2; curing at room temperature for 4 hours, curing at 60°C for 4 hours, and then Crush it and grind it with a vibrating mill, and the fineness is greater than 400 mesh.

黑色颜料对混凝土的渗透性影响很大，并且随着掺量的增加，牡蛎幼虫附着量减少。一方面是由于混凝土渗透性增加，增大了混凝土的碱的渗出，另一方面，可能由于其中的铁氧化物转换为铁离子，导致铁离子浓度增加，会抑制牡蛎幼虫的附着。针对该问题，采用树脂包覆颜料后，再粉磨成粉末，可以大幅度提高混凝土的抗渗性，特别是掺量为1.37％时，其电通量仅增加3.2％。同时随着深色颜料的增加，牡蛎附着持续增加，不同于改性前在掺量为1.37％，表现为牡蛎幼虫附着率下降。The black pigment has a great influence on the permeability of concrete, and with the increase of the content, the attachment of oyster larvae decreases. On the one hand, due to the increase in concrete permeability, the alkali exudation of the concrete is increased. On the other hand, the iron oxides in the concrete may be converted into iron ions, resulting in an increase in the concentration of iron ions, which will inhibit the attachment of oyster larvae. To solve this problem, the resin coated pigments and then ground into powder can greatly improve the impermeability of concrete, especially when the content is 1.37%, the electric flux only increases by 3.2%. At the same time, with the increase of dark pigments, the attachment of oysters continued to increase, which was different from the 1.37% content before modification, which showed that the attachment rate of oyster larvae decreased.

实施例9：未改性牛骨粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、10.26％、0.79％、5.54％、46.67％、29.0％、7.2％、0.03％。Example 9: The weight ratios of unmodified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water, and polycarboxylic acid water-reducing agent powder are: 0.51%, 10.26%, 0.79 %, 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例10：未改性牛骨粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、10.26％、0.75％、5.23％、46.67％、29.0％、7.2％、0.03％。Example 10: The weight ratios of unmodified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water, and polycarboxylate water-reducing agent powder are: 0.86%, 10.26%, 0.75 %, 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例11：未改性牛骨粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、10.26％、0.68％、4.79％、46.67％、29.0％、7.2％、0.03％。Example 11: The weight ratios of unmodified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 1.37%, 10.26%, 0.68 %, 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例12：改性牛骨粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、10.26％、0.79％、5.54％、46.67％、29.0％、7.2％、0.03％。Example 12: The weight ratios of modified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 0.51%, 10.26%, 0.79%. , 5.54%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例13：改性牛骨粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、10.26％、0.75％、5.23％、46.67％、29.0％、7.2％、0.03％。Example 13: The weight ratio of modified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, gravel, sand, water and polycarboxylic acid water-reducing agent powder is 0.86%, 10.26%, 0.75%, respectively , 5.23%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例14：改性牛骨粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、10.26％、0.68％、4.79％、46.67％、29.0％、7.2％、0.03％。Example 14: The weight ratios of modified bovine bone powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, sand, water and polycarboxylic acid water reducer powder are: 1.37%, 10.26%, and 0.68%. , 4.79%, 46.67%, 29.0%, 7.2%, 0.03%.

将100目的牛骨粉加入到浓度2％的磷酸溶液，两者的重量比为1:3，温度为20～30℃，在转速为200～500转/分搅拌器内搅拌30分钟，采用3000～5000转/分的离心机离心3分钟，倒掉上清液，并用水清洗离心后的固体物质的固体物质2～3次，洗涤水不再显示酸性；将离心后的固体物质在40℃真空干燥，将干燥的牛骨粉与矿渣粉按1:4混合，用振动磨粉磨到细度大于200目，待用。Add 100 mesh beef bone meal to a 2% phosphoric acid solution, the weight ratio of the two is 1:3, the temperature is 20 ~ 30 ℃, and the rotation speed is 200 ~ 500 rpm in a stirrer for 30 minutes, using 3000 ~ Centrifuge the centrifuge at 5000 rpm for 3 minutes, discard the supernatant, and wash the solid material after centrifugation with water for 2 to 3 times, the washing water no longer shows acidity; the solid material after centrifugation is vacuumed at 40°C Dry, mix the dried beef bone powder and slag powder in a ratio of 1:4, grind it with a vibration mill to a fineness of more than 200 meshes, and set aside.

注：将改性牛骨粉细度粉磨到200目～300目Note: Grind the modified beef bone meal to a fineness of 200 mesh to 300 mesh

针对牛骨粉粉磨难度大，一般在100目左右就很难再继续粉磨，这里通过先采用浓度为2％的稀磷酸对80目的牛骨粉进行化学改性，然后将干燥的牛骨粉与1:4的矿渣粉，用振动磨粉磨到细度大于200目。这样改性后的牛骨粉，增大了其与混凝土中碱性物质的接触，同时混凝土内部的微观结构更加致密，没出现前面所出现的发霉现象。且经改性后，渗透性在低掺量的情况下，混凝土的抗渗性还有所改善。即使掺量达到1.37％，其电通量增加只有4.2％，以及牡蛎幼虫的附着变化率从205％增加到400％。In view of the difficulty in grinding beef bone meal, it is generally difficult to continue grinding at about 100 mesh. Here, the 80 mesh beef bone meal is chemically modified by using dilute phosphoric acid with a concentration of 2%, and then the dried beef bone meal is combined with 1 : 4 slag powder, use a vibration mill to grind to a fineness greater than 200 mesh. In this way, the modified bovine bone meal increases its contact with the alkaline substances in the concrete, and at the same time, the internal microstructure of the concrete is denser, without the moldy phenomenon that appeared before. And after modification, the permeability of concrete is improved even at low dosage. Even if the dosage reaches 1.37%, the electric flux increases by only 4.2%, and the attachment change rate of oyster larvae increases from 205% to 400%.

实施例15：改性牛骨粉、改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、牡蛎壳粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、0.86％、0.51％、10.26％、0.62％、4.34％、46.67％、29.0％、7.2％、0.03％。Example 15: Modified beef bone powder, modified dark pigment (iron oxide black: aniline black mixture mass ratio = 1:1), oyster shell powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, The weight ratio of sand, water and polycarboxylic acid water reducing agent powder is 0.51%, 0.86%, 0.51%, 10.26%, 0.62%, 4.34%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例16：改性牛骨粉、改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、牡蛎壳粉、普通硅酸盐水泥、硅灰、高炉矿渣粉、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、0.86％、0.51％、10.26％、0.58％、4.03％、46.67％、29.0％、7.2％、0.03％。Example 16: Modified beef bone powder, modified dark pigment (mass ratio of iron oxide black: aniline black mixture = 1:1), oyster shell powder, ordinary Portland cement, silica fume, blast furnace slag powder, crushed stone, The weight ratio of sand, water and polycarboxylic acid water reducing agent powder is 0.86%, 0.86%, 0.51%, 10.26%, 0.58%, 4.03%, 46.67%, 29.0%, 7.2%, 0.03%.

本实例通过在基准混凝土的基础上，复合掺加深色颜料、牡蛎壳粉、牛骨粉，通过基准混凝土为牡蛎附着、***提供必要的Ca ²⁺，且具有较低的碱度；同时深色颜料使混凝土颜色变深，吸收了几乎所有的可见光，混凝土表面变为黑色，提供了阴暗的环境；掺加贝壳粉和牛骨粉提供其附着必需的HCO ₃ ^2-、PO ₄ ^3-，以及各种微量元素，共同促进牡蛎的附着，使得牡蛎幼虫在深色颜料为0.86％、牡蛎壳粉为0.51％、牛骨粉0.51％时，其附着变化率可达317％，当深色颜料为0.86％、牡蛎壳粉为0.51％、牛骨粉0.86％时，附着变化率增幅为517％。 In this example, on the basis of the reference concrete, it is compounded with dark pigments, oyster shell powder, and beef bone powder to provide the necessary Ca ²⁺ for the attachment and metamorphosis of the oysters through the reference concrete, and it has a lower alkalinity; at the same time, the dark pigments The color of the concrete becomes darker and almost all visible light is absorbed. The surface of the concrete becomes black, providing a dark environment; adding shell powder and beef bone powder to provide the necessary HCO ₃ ^2- , PO ₄ ^3- for its attachment, and various traces The elements promote the attachment of oysters together, so that when the dark pigment is 0.86%, the oyster shell powder is 0.51%, and the beef bone meal is 0.51%, the adhesion change rate can reach 317%. When the dark pigment is 0.86%, the oyster When shell powder is 0.51% and beef bone powder is 0.86%, the increase in adhesion change rate is 517%.

实施例1～16实施方法具体操作步骤如下：The specific operation steps of the implementation methods of Examples 1-16 are as follows:

按照上述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土的制备方法，制备3个Φ100×50mm圆柱体试件和10块200×200×30mm长方体试件，分别用于测试该混凝土28d抗氯离子渗透性和标准养护28d后实验室内牡蛎幼虫附着***情况。具体操作步骤如下：According to the above-mentioned preparation method of dark Portland cement concrete that induces the adhesion of marine sessile organisms, 3 Φ100×50mm cylindrical specimens and 10 200×200×30mm cuboid specimens were prepared to test the concrete. Resistance to chloride ion penetration at 28 days and the attachment and metamorphosis of oyster larvae in the laboratory after 28 days of standard curing. The specific steps are as follows:

(一)试件成型(1) Specimen molding

1、计算并按照上述的质量精确称量普通硅酸盐水泥、矿物掺合料、碎石、砂、水、深色颜料、生物钙粉和聚羧酸减水剂粉。1. Calculate and accurately weigh ordinary Portland cement, mineral admixtures, gravel, sand, water, dark pigments, biological calcium powder and polycarboxylic acid water-reducing agent powder according to the above-mentioned mass.

2、先将碎石和砂放入混凝土搅拌机中搅拌0.5～1分钟；然后加入硅酸盐水泥、矿物掺合料、生物钙粉、深色颜料，再继续搅拌0.5～1分钟；然后加入水和超塑化剂搅拌2～6分钟；搅拌均匀后，进行浇筑、振捣、拆模，即可制得3个Φ100×50mm圆柱体试件和5块200×200×30mm长方体试件；最后将其放入标准养护室持续28d，并在各龄期进行相应的渗透性能评价，以及在28d后进行实验室内牡蛎幼虫附着、***实验。2. Put the gravel and sand into the concrete mixer and mix for 0.5 to 1 minute; then add Portland cement, mineral admixtures, biological calcium powder, and dark pigments, and continue to mix for 0.5 to 1 minute; then add water Stir with the superplasticizer for 2-6 minutes; after stirring evenly, pour, vibrate, and remove the mold to obtain 3 Φ100×50mm cylindrical specimens and 5 200×200×30mm rectangular parallelepiped specimens; finally Put it in a standard curing room for 28 days, and conduct corresponding evaluations of permeability at each instar, and perform oyster larva attachment and metamorphosis experiments in the laboratory after 28 days.

(二)快速氯离子渗透实验具体步骤如下：(2) The specific steps of the rapid chloride ion permeation experiment are as follows:

根据标准《Standard Test Method for Electrical Indication of Concrete’s Ability to Resist Chloride Ion Penetration》(ASTM1202-2017)，标准养护28d时，分别从养护室中取出3个Φ100×50mm圆柱体试件，并将其表面水分及杂物清理干净，待其表面干燥后在圆柱体试件侧面涂刷一薄层环氧树脂。然后将试件放入真空饱水机中持续20至24h。然后取出试件清理表面，并将其置于有机玻璃模具中，同时检测试件与模具之间密封性后，在其两侧模具之中分别装入质量浓度为3％的氯化钠溶液(电极连电源负极)和摩尔浓度为0.3mol/L的氢氧化钠溶液(电极连电源正极)。接着启动实验仪器，在6h后记录实验数据，后两个试件重复上述操作。最后根据规范进行强度计算。According to the standard "Standard Test Method for Electrical Indication of Concrete's Ability to Resist Chloride Ion Penetration" (ASTM1202-2017), when the standard is cured for 28 days, three Φ100×50mm cylindrical specimens are taken out from the curing room and their surface moisture Clean up the sundries, and paint a thin layer of epoxy resin on the side of the cylindrical specimen after the surface is dry. Then put the test piece into the vacuum water saturated machine for 20 to 24 hours. Then take out the test piece to clean the surface, and place it in the plexiglass mold. At the same time, after testing the tightness between the test piece and the mold, put a sodium chloride solution with a mass concentration of 3% in the molds on both sides ( The electrode is connected to the negative pole of the power supply) and a sodium hydroxide solution with a molar concentration of 0.3 mol/L (the electrode is connected to the positive pole of the power supply). Then start the experimental instrument, record the experimental data after 6h, and repeat the above operation for the last two test pieces. Finally, the strength calculation is carried out according to the specification.

(三)室内牡蛎幼虫附着***实验具体步骤如下：(3) The specific steps of indoor oyster larvae attachment and metamorphosis experiment are as follows:

标准养护28d后，分别从养护室中取出200×200×30mm长方体试件，并将其表面水分及杂物清理干净，随后放入试验池中，并且实验室内准备试验池，牡蛎幼虫丰度为0.85ind/ml ³，池中海水为砂滤后的黄海海水，盐度约为32％～34％，待海水水位高于混凝土试件后，将氧气管均匀散布在试验池中，准备牡蛎幼虫投放。将牡蛎幼虫在水桶中缓慢搅拌均匀后，使用烧杯准确称量含有牡蛎幼虫的海水质量，接着将其均匀分布于试验池中。 After 28 days of standard curing, take out the 200×200×30mm cuboid specimens from the curing room, clean the surface water and debris, and then put them in the test pool, and prepare the test pool in the laboratory. The abundance of oyster larvae It is 0.85ind/ml ³ , the seawater in the pond is the Yellow Sea seawater after sand filtration, and the salinity is about 32% to 34%. After the seawater level is higher than the concrete specimen, the oxygen pipes are evenly distributed in the test pond to prepare oysters Larvae are released. After slowly stirring the oyster larvae in a bucket, use a beaker to accurately weigh the quality of the seawater containing the oyster larvae, and then distribute them evenly in the test tank.

并在诱导牡蛎附着试验开始后，将试验池内海水每日进行更换，换水量为试验池总容量的1/3，使用筛网(≥200目)堵在排水口，防止未附着的牡蛎幼苗随水流失，将筛网上的幼苗再次投放到试验池中，之后每日9时及19时使用胶头滴管定时定量投喂小球藻，并观察牡蛎附着情况。After the start of the oyster attachment test, the seawater in the test pool was replaced daily. The amount of water changed was 1/3 of the total capacity of the test pool. A screen (≥200 mesh) was used to block the drain to prevent unattached oyster seedlings from following. After the water is lost, the seedlings on the sieve are put into the test pond again, and then the chlorella is regularly and quantitatively fed with a rubber-tip dropper at 9 o'clock and 19 o'clock every day, and the attachment of oysters is observed.

试验持续30d后，将试验池中的水排出，取出试件，对试件表面牡蛎数目及成活率进行统计记录分析，统计时取混凝土浇筑成型时光滑的底面。After the test lasts for 30 days, drain the water in the test pool, take out the test piece, and analyze the number of oysters on the surface of the test piece and the survival rate. The statistics take the smooth bottom surface when the concrete is poured.

与对比文件1(一种新型混凝土人工鱼礁及其制备方法CN104529286A)相比，区别在于：Compared with Comparative Document 1 (a new type of concrete artificial reef and its preparation method CN104529286A), the difference lies in:

本发明中的目的与对比文件不同：对比文件1虽然在混凝土中掺加牡蛎壳粉，但它的目的是废弃物利用，修复和完善人工鱼礁。而本发明的目的是诱导固着生物附着，主要为牡蛎，在潮差区钢筋混凝土防腐蚀时，考虑藤壶的附着。The purpose of the present invention is different from the comparison document: Although the comparison document 1 is mixed with oyster shell powder in the concrete, its purpose is to use waste, repair and improve the artificial reef. The purpose of the present invention is to induce the attachment of sessile organisms, mainly oysters, and the attachment of barnacles is considered when the reinforced concrete is anti-corrosive in the tidal range.

与对比文件2(一种仿生混凝土人工鱼礁及其制备方法2015CN104938384A)相比，区别在于：Compared with Comparative Document 2 (a bionic concrete artificial reef and its preparation method 2015CN104938384A), the difference is:

(1)本发明中的目的与对比文件2不同：对比文件2虽然在混凝土中掺加牡蛎壳或牡蛎壳粉，但它的目的主要通过表面的仿生性来实现，集鱼、集微生物、藻类，增加微生物数量改善水体环境，未提及牡蛎。而本发明的目的是诱导固着生物附着，主要为牡蛎，在潮差区钢筋混凝土防腐蚀时，考虑藤壶的附着。(1) The purpose of the present invention is different from that of Comparative Document 2: Although Comparative Document 2 is mixed with oyster shells or oyster shell powder in the concrete, its purpose is mainly realized by the surface bionics, collecting fish, microorganisms, and algae. , Increase the number of microorganisms and improve the water environment, without mentioning oysters. The purpose of the present invention is to induce the attachment of sessile organisms, mainly oysters, and the attachment of barnacles is considered when the reinforced concrete is anticorrosive in the tidal range.

(2)对比文件2指出，水泥掺量10％以下的生物碳酸钙粉(150～200目)对诱导附着不明显。但本发明在研究过程中采用改性的牛骨粉与生物碳酸钙粉(细度：100～1000目)，得到了牛骨粉和生物碳酸钙粉的最适掺量为胶凝材料的10％以内。(2) Comparative Document 2 points out that biological calcium carbonate powder (150-200 mesh) with a cement content of less than 10% is not obvious for inducing adhesion. However, in the present invention, modified beef bone powder and biological calcium carbonate powder (fineness: 100-1000 mesh) are used in the research process, and the optimum blending amount of beef bone powder and biological calcium carbonate powder is within 10% of the gelling material. .

(3)通过对牛骨粉和生物碳酸钙粉的改性，具体为对100目到500目间的鸡蛋壳粉、珊瑚粉、牡蛎壳粉、鱼骨粉采用以下酸进行处理，包括乙酸、醋酸、硅酸、亚硫酸中的一种或两种；对100目到500目牛骨粉采用以下酸处理，包括稀释的磷酸、硫酸、盐酸和硝酸的一种或两种。(3) Through the modification of beef bone meal and biological calcium carbonate powder, specifically the following acids are used to treat egg shell powder, coral powder, oyster shell powder, and fish bone powder between 100 mesh and 500 mesh, including acetic acid, acetic acid, One or two of silicic acid and sulfurous acid; 100 mesh to 500 mesh cattle bone meal is treated with the following acids, including one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

(4)对比文件在混凝土表面镶嵌牡蛎壳施工困难，也并不是每个工程表面都能采用这样的方法，可行性低。本发明在混凝土内中加入贝壳粉以诱导固着生物附着，且贝壳粉的掺量占胶凝材料质量的10％以下，不仅施工简单还能大幅度增加牡蛎附着量。(4) It is difficult to inlay oyster shells on the concrete surface, and it is not feasible for every project surface to adopt this method. The feasibility is low. In the present invention, shell powder is added to the concrete to induce the attachment of fixed organisms, and the mixing amount of the shell powder accounts for less than 10% of the mass of the cementing material, which is not only simple in construction, but also can greatly increase the attachment of oysters.

(5)海洋环境下，近年来出现了多次的人工鱼礁腐蚀严重的现象，主要受厌氧微生物硫杆菌分泌的生物硫酸和其它细菌分泌的酸性物质等共同作用造成了严重的腐蚀。而碳酸钙抗酸腐蚀的能力很弱，因此，细度较大的碳酸钙含量过高会造成严重的酸腐蚀。(5) In the marine environment, many artificial reefs have experienced serious corrosion in recent years. The biological sulfuric acid secreted by the anaerobic microorganism Thiobacillus and the acidic substances secreted by other bacteria have caused serious corrosion. The ability of calcium carbonate to resist acid corrosion is very weak. Therefore, the high content of calcium carbonate with larger fineness will cause serious acid corrosion.

与对比文件3(范瑞良.基质类型对牡蛎附着、生长、种群建立及礁体发育的影响[D])相比，区别在于：Compared with Comparative Document 3 (Fan Ruiliang. The influence of substrate type on oyster attachment, growth, population establishment and reef development [D]), the differences are:

(1)对比文件3，使用了80目的牛骨粉、钙粉和石膏粉，分别单独掺加于混凝土中。本发明中所有的钙质材料的细度均大于100目，大于对比文件3中的材料细度。同样是掺加了牛骨粉，但与生物碳酸钙粉，如牡蛎壳粉、鸡蛋壳粉、鱼骨粉、珊瑚粉中的一种或者多种复合掺加。目的是在考虑混凝土颗粒级配的同时，也要充分发挥它们的诱导能力。(1) Comparative Document 3 uses 80 mesh beef bone powder, calcium powder and gypsum powder, which are separately mixed into concrete. The fineness of all the calcareous materials in the present invention is greater than 100 mesh, which is greater than the material fineness in the reference document 3. It is also mixed with beef bone powder, but mixed with biological calcium carbonate powder, such as one or more of oyster shell powder, egg shell powder, fish bone powder, and coral powder. The purpose is to give full play to their inducing ability while considering the gradation of concrete particles.

(2)常温条件下，用振动磨进行牛骨粉的粉磨，当细度大于80目后，由于牛骨粉含有大量的胶原蛋白，结团严重，无法继续粉磨。本发明中采用了稀酸改性技术，并与其它物质复合粉磨，得到了粒径小的牛骨粉，细度＞200目的改性生物钙粉。所制备的生物钙粉，保留了生物钙的原有的物质，并增大了其诱导牡蛎幼虫附着物质的释放速率，并降低生物钙粉掺量，从而降低对水泥混凝土性能的影响。(2) Under normal temperature conditions, use a vibration mill to grind beef bone meal. When the fineness is greater than 80 mesh, because the beef bone meal contains a large amount of collagen, the agglomeration is serious and the grinding cannot be continued. In the present invention, the dilute acid modification technology is used and combined with other substances to be ground to obtain modified biological calcium powder with a small particle size and a fineness of more than 200 meshes. The prepared bio-calcium powder retains the original substance of bio-calcium, increases the release rate of the substance that induces the attachment of oyster larvae, and reduces the amount of bio-calcium powder, thereby reducing the impact on the performance of cement concrete.

(3)由于牛骨粉中含有丰富的胶原蛋白等有机物质，这些物质的大量掺入会引起混凝土强度和抗渗性下降，特别是超过5％后，增大掺量，混凝土强度迅速下降、抗渗性显著变差，以及标准养护条件下混凝土表面会长霉。图1是混凝土试件发霉的情况。图2为改性后混凝土的表面情况。(3) Because bovine bone meal is rich in organic substances such as collagen, a large amount of these substances will cause the strength and impermeability of concrete to decrease, especially if it exceeds 5%, increase the amount of concrete, and the strength of concrete will decrease rapidly. The permeability is significantly worse, and the surface of the concrete will grow mildew under standard curing conditions. Figure 1 shows the mold on the concrete specimen. Figure 2 shows the surface of the modified concrete.

从图1中可以看出，混凝土表面的霉呈白色絮状，几乎覆盖了整个混凝土表面；相同的牛骨粉掺量、龄期、养护条件，图2中的混凝土表面则没有发霉。It can be seen from Figure 1 that the mold on the surface of the concrete is white flocculent, covering almost the entire surface of the concrete; with the same amount of bovine bone meal, age, and curing conditions, there is no mold on the surface of the concrete in Figure 2.

本发明通过控制采用稀酸改性和复合粉磨技术，充分发挥牛骨粉的诱导能力，大幅度降低牛骨粉掺量，并进行防腐蚀处理及改性，实现了以牛骨粉为主的复合诱导剂，其掺量小，几乎不影响混凝土强度和渗透性，同时具有很强的牡蛎幼虫附着能力，且解决了混凝土的发霉问题。相对于不掺加诱导剂的混凝土，掺加诱导剂的混凝土牡蛎幼虫附着个数明显增加。By controlling the use of dilute acid modification and composite grinding technology, the present invention gives full play to the inducing ability of bovine bone powder, greatly reduces the amount of bovine bone powder, and carries out anti-corrosion treatment and modification, and realizes the compound induction based on bovine bone powder. It has a small content and hardly affects the strength and permeability of concrete. At the same time, it has strong adhesion of oyster larvae and solves the problem of mildew in concrete. Compared with the concrete without the inducer, the number of oyster larvae on the concrete with the inducer increased significantly.

对比文件及查阅到的文献资料表明：钙含量对牡蛎幼虫的附着至关重要，同样目前一些实验结果也证明在水泥基材料中掺加适量的碳酸钙质的物质可以促进牡蛎幼虫的附着及生长。但是水泥混凝土中有大量的钙离子，孔溶液中的pH值一般大于12.5，饱和氢氧化钙溶液的pH值在常温约为12，所以混凝土孔溶液中的钙离子浓度约5mmol/L；而碳酸钙的溶解度很小，在25℃时只有9.5×10 ^-5mol/L(9.5×10 ^-2mmol/L)。目前认为诱导牡蛎附着的钙离子浓度最佳范围为10～25mmol/L，即使将牡蛎幼虫放置在饱和的碳酸钙溶液中，也没有足够的Ca ²⁺浓度为牡蛎附着提供适宜的离子浓度。进一步说，水泥混凝土内部的Ca(OH) ₂可以较快的释放出来，而碳酸钙的溶解则需要较长的时间。因此，可以确定在混凝土中掺入碳酸钙质材料促进牡蛎幼虫的附着，Ca ²⁺不是起主导作用。牡蛎的早期附着、***与HCO ₃ ^-有关，在***时和Ca ²⁺一起生成碳酸钙的次生壳。掺加碳酸钙后，由于碳酸钙与CO ₂和水反应，生成Ca(HCO ₃) ₂后参与附着，是其对牡蛎幼虫附着促进的根本机理。 The comparative documents and the literature data that have been consulted show that the calcium content is very important for the attachment of oyster larvae. Similarly, some current experimental results also prove that adding an appropriate amount of calcium carbonate to cement-based materials can promote the attachment and growth of oyster larvae. . However, there are a lot of calcium ions in cement concrete. The pH value in the pore solution is generally greater than 12.5. The pH value of the saturated calcium hydroxide solution is about 12 at room temperature, so the calcium ion concentration in the concrete pore solution is about 5mmol/L; The solubility of calcium is very small, only 9.5×10 ^-5 mol/L (9.5×10 ^-2 mmol/L) at 25°C. At present, it is believed that the best range of calcium ion concentration for inducing oyster attachment is 10-25mmol/L. Even if oyster larvae are placed in a saturated calcium carbonate solution, there is not enough Ca ²⁺ concentration to provide a suitable ion concentration for oyster attachment. Furthermore, the Ca(OH) ₂ inside the cement concrete can be released quickly, while the dissolution of calcium carbonate takes a longer time. Therefore, it can be determined that calcium carbonate is added to concrete to promote the attachment of oyster larvae, and Ca ²⁺ does not play a leading role. The early attachment and metamorphosis of oysters are related to HCO ₃ ^- , and ^{together with Ca 2+,} they form secondary shells of calcium carbonate. After adding calcium carbonate, the calcium carbonate _{reacts with CO 2} and water to form Ca(HCO ₃ ) ₂ and participate in the attachment, which is the fundamental mechanism for promoting the attachment of oyster larvae.

水泥基材料中碳酸钙掺量有一个最适掺量，可以从以下三方面进行解释：There is an optimal dosage of calcium carbonate in cement-based materials, which can be explained from the following three aspects:

1)对于等量取代水泥，随着碳酸钙掺量的增加，混凝土中的碱被稀释，总的碱度在降低，但是随着碳酸钙掺量的增加，混凝土中的碳酸钙溶解几率增大，其溶液中的HCO ₃ ^-含量增加，所以促进牡蛎的附着与***；但是掺量过大时，混凝土的渗透性急剧增大，混凝土中的碱和碳酸根快速渗出，使得碱的负面效应凸显，而碳酸根的临界或者负面效应初显，所以表现为附着量降低； 1) For the equivalent replacement of cement, as the content of calcium carbonate increases, the alkali in the concrete is diluted and the total alkalinity decreases, but as the content of calcium carbonate increases, the probability of dissolution of calcium carbonate in the concrete increases. , The HCO ₃ ^- content in the solution increases, so it promotes the adhesion and metamorphosis of the oysters; but when the amount is too large, the permeability of the concrete increases sharply, and the alkali and carbonate in the concrete quickly seep out, making the negative effect of the alkali It is prominent, and the critical or negative effect of carbonate is beginning to appear, so it shows that the amount of adhesion is reduced;

2)对于等量取代骨料，其随着掺量的增加，混凝土的渗透性下降，会导致钙离子及OH ^-的渗出减少，但碳酸根离子的渗透速率会先渐增大，到达一定值时，表现为牡蛎附着达到最大值；而随着掺量继续增大，则钙离子下降幅度大，而碳酸根则也可能会降低，会出现钙离子浓度限制牡蛎幼虫的附着，表现为附着量降低； 2) For the same amount of replacement aggregate, as the content increases, the permeability of the concrete decreases, which will lead to ^{a decrease in the exudation of calcium ions and OH -} , but the permeation rate of carbonate ions will first increase and reach a certain level. When the value is higher, it shows that the adhesion of oysters reaches the maximum; and as the dosage continues to increase, the calcium ion declines greatly, while carbonate may also decrease, and the calcium ion concentration will limit the adhesion of oyster larvae, which appears as adhesion Volume reduction

3)对于等量取代矿物掺合料，同样随着掺量的增加，渗透性在增加，且由于碳酸钙的增加，使牡蛎附着要求所需的HCO ₃ ^-浓度达到了一个合适范围，表现为牡蛎幼虫附着增加；随着矿物掺合料掺量继续增大，降低了矿物掺合料的掺量，从而渗出的碱量增加，碳酸根增加，但过多的碱及HCO ₃ ^-离子会抑制牡蛎幼虫附着。 3) for an equal amount of mineral admixtures substituted, with the increase in the same dosage, the permeability increases, and the increase of calcium carbonate, so that the desired adhesion oyster claim HCO ₃ ^- concentration of a suitable range, the performance of The attachment of oyster larvae increases; as the amount of mineral admixtures continues to increase, the amount of mineral admixtures is reduced, so that the amount of alkali exuded increases, and carbonate increases, but too much alkali and HCO ₃ ^- ions will Inhibit the attachment of oyster larvae.

与对比文件4(李真真,公丕海,关长涛,et al.不同水泥类型混凝土人工鱼礁的生物附着效果[J].渔业科学进展,2017,38(5):57-63.)相比，区别在于：Compared with Comparative Document 4 (Li Zhenzhen, Gongpihai, Guan Changtao, et al. The biological attachment effect of different cement types in concrete artificial reefs[J]. Fishery Science Progress,2017,38(5):57-63.), The difference is that:

对比文件4中的混凝土用于富集海洋生物，其主要从附着生物量的大小和多样性出发，主要附着的生物为各种藻类等。本发明中研究目的则是诱导牡蛎附着，但是牡蛎和藤壶对碱度的耐受性要高于藻类，并且牡蛎的附着、***需要大量的钙离子，所以说两种混凝土看似一样，实则存在很大区别。图3和图4分别是对比文件4经过210d左右的实海附着实验和本发明经过300d的实海附着实验后生物附着的情况对比。The concrete in Comparative Document 4 is used to enrich marine organisms, which mainly starts from the size and diversity of attached biomass, and the main attached organisms are various algae. The research purpose of the present invention is to induce the attachment of oysters, but the tolerance of oysters and barnacles to alkalinity is higher than that of algae, and the attachment and metamorphosis of oysters require a large amount of calcium ions, so the two concretes seem to be the same, but in reality There is a big difference. Figures 3 and 4 are respectively a comparison of the biological attachment of the comparative document 4 after the actual sea attachment experiment of about 210 days and the present invention after the actual sea attachment experiment of 300 days.

对比文件4中使用了复合硅酸盐水泥、矿渣硅酸盐水泥、火山灰质硅酸盐水泥、粉煤灰硅酸盐水泥和铝酸盐水泥：本发明中采用了普通硅酸盐水泥与矿物掺合料的复合掺加来实现低碱度水泥；其中硅灰是矿物掺合料中一种活性高，适宜掺量对海洋环境下钢筋混凝土耐久性提升效果明显，通过优化设计及实验，可以得到强度和耐久性均优的低碱度水泥。同时利用硅灰混凝土的高抗渗性特点，即使混凝土内部碱度较高，仍有大量的牡蛎幼虫附着、***及生长。此外，海洋植物和牡蛎、藤壶等固着生物耐碱能力不同，且在附着期及后期需要的环境不同，如藤壶和牡蛎的附着、***及后期生长都需要大量的钙离子。In Comparative Document 4, composite Portland cement, slag Portland cement, pozzolanic Portland cement, fly ash Portland cement and aluminate cement are used: ordinary Portland cement and minerals are used in the present invention. The compound admixture of admixtures is used to achieve low alkalinity cement; among them, silica fume is a kind of mineral admixture with high activity, and the appropriate amount of admixture has a significant effect on the durability of reinforced concrete in the marine environment. Through optimized design and experiments, it can be A low alkalinity cement with excellent strength and durability is obtained. At the same time, taking advantage of the high impermeability characteristics of silica fume concrete, even if the internal alkalinity of the concrete is high, there are still a large number of oyster larvae attached, metamorphosed and growing. In addition, marine plants and oysters, barnacles and other sessile organisms have different alkali resistance capabilities, and require different environments during the attachment period and later period. For example, barnacles and oysters require a large amount of calcium ions for attachment, metamorphosis, and late growth.

因此，由于这部分知识涉及到海洋固着生物、海洋植物与海洋混凝土工程学科的交叉，无论是混凝土及工程领域或者海洋生物领域的技术人员，无法通过对比文件1而获得本发明中的将混凝土碱度降低与钙离子浓度之间的平衡与海洋固着生物的附着紧密关联的技术特征。Therefore, since this part of knowledge involves the intersection of marine sessile organisms, marine plants and marine concrete engineering disciplines, no matter the technical personnel in the concrete and engineering fields or marine biology fields, they cannot obtain the concrete alkali in the present invention through the reference document 1. It is a technical feature that the balance between temperature reduction and calcium ion concentration is closely related to the attachment of marine sessile organisms.

另外，本发明中独有的特点及其具有的有益效果如下：In addition, the unique features and beneficial effects of the present invention are as follows:

深色颜料：Dark pigments:

利用牡蛎眼点幼虫的避光特性，采用深色颜料(氧化铁黑、苯胺黑、炭黑、硫化锑、氧化铁红、有机颜料红中的一种或两种)掺入混凝土中，改变混凝土的颜色，使混凝土的颜色变深，让牡蛎幼虫认为就是黑暗环境，诱导牡蛎幼虫自行到达深色的混凝土表面，增加幼虫与混凝土表面的接触几率，实现牡蛎幼虫诱导附着率增加。具体为：Taking advantage of the light-shielding properties of oyster eye-spot larvae, dark pigments (one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red, and organic pigment red) are mixed into concrete to change the concrete The color of the concrete darkens the color of the concrete and makes the oyster larvae think it is a dark environment. It induces the oyster larvae to reach the dark concrete surface by themselves, increases the chance of contact between the larvae and the concrete surface, and achieves an increase in the induced attachment rate of the oyster larvae. Specifically:

海洋生物研究人员，为了养殖增殖或者是为了消除不期望出现的种群等情况下，考虑了采用不同颜色的底质对海洋固着生物的附着的研究，属于海洋生物学科。和海洋混凝土工程或者混凝土材料学科相差较大，完全是两个大的学科。通过海洋固着生物与混凝土学科的交叉，得到了采用深色混凝土进行牡蛎幼虫的诱导附着。本发明中采用添加深色颜料，用加深混凝土表面的颜色来促进牡蛎幼虫的附着。混凝土中掺入其它的材料，都会对混凝土的性能产生影响。本发明考虑到不同水泥的混凝土，其表面的颜色均有差异。因此，根据水泥的类型和掺量来确定深色物质的掺量。深色颜料也会影响混凝土的性能。最为重要的是，掺加深色颜料的同时，若不控制混凝土中的碱和Ca ²⁺等渗透速率，释放出的碱会影响固着生物幼虫的附着、***及生长，就会出现掺量大于一定值时，幼虫附着量有所降低。本发明中对混凝土的抗渗性进行了设计和控制，主要措施为：深色颜料类型的选取、掺加量的控制及进行改性。随着深色物质掺量的增加，幼虫附着率先增大，当掺量为胶凝材料的0.5％～6％时，幼虫的附着量最大，但之后小幅增加或者保持不变。 Marine biology researchers, for the purpose of breeding and proliferating or eliminating undesirable populations, consider the use of different colored substrates to study the attachment of marine sessile organisms, belonging to the Department of Marine Biology. It is quite different from marine concrete engineering or concrete materials disciplines, and they are completely two major disciplines. Through the intersection of marine sessile organisms and concrete disciplines, dark concrete is used to induce the attachment of oyster larvae. In the present invention, dark pigments are added to deepen the color of the concrete surface to promote the attachment of oyster larvae. Other materials mixed into concrete will have an impact on the performance of concrete. The present invention takes into account that different cement concretes have different surface colors. Therefore, according to the type and amount of cement to determine the amount of dark substance. Dark pigments can also affect the performance of concrete. The most important thing is that while adding dark pigments, if the ^{penetration rate of alkali and Ca 2+} in the concrete is not controlled, the released alkali will affect the attachment, metamorphosis and growth of the fixed biological larvae, and the dosage will be greater than a certain amount. At the value, the amount of larvae attached is reduced. In the present invention, the impermeability of concrete is designed and controlled, and the main measures are: the selection of the type of dark pigment, the control of the addition amount, and the modification. With the increase of the dark substance content, the attachment rate of the larvae increases first. When the blending amount is 0.5% to 6% of the gelling material, the attachment amount of the larvae is the largest, but thereafter it increases slightly or remains unchanged.

混凝土渗透性：Concrete permeability:

混凝土的强度和渗透性是混凝土最主要的两个性能。而在基准混凝土中掺加不同的诱导剂，都会对混凝土性能产生影响，因此，在考虑掺加不同物质促进牡蛎幼虫附着、***及后期生长时，首先一定要从整体控制其对混凝土的强度和渗透性不产生大的影响，然后再根据各种原材料的配伍性去选择原材料，当原材料性能不能满足实际要求时，则通过对原材料的改性后再加入，从而达到我们期望的功能。但实际上，前述的相关研究虽然考虑到了钙质的掺量对牡蛎幼虫附着的影响，但是不考虑混凝土本身的性能，不去考虑水灰比以及钙质的掺量以及养护等，而混凝土渗透性的变化会使混凝土内部碱和离子渗漏的速率改变，混凝土的抗渗性越差，其内部的碱和离子的渗漏速率越大，可能是指数形式的增长。因此，这些释放出来的碱和离子会对幼虫产生很大影响，可能出现从促进附着变为抑制附着的情况，特别水泥掺量大时，这种情况会更严重。因此，混凝土中掺加诱导剂，一定要保证混凝土的抗渗性的变化在可控的范围内，如变化不超过10％。这样才能对这些的诱导效果进行比较，否则的话，则无法评价单掺诱导剂或者诱导剂复合掺加对牡蛎幼虫诱导效果的影响。The strength and permeability of concrete are the two most important properties of concrete. The addition of different inducers to the benchmark concrete will have an impact on the performance of the concrete. Therefore, when considering the addition of different substances to promote the attachment, metamorphosis and later growth of the oyster larvae, the overall strength and strength of the concrete must be controlled first. The permeability does not have a big impact, and then select the raw materials according to the compatibility of various raw materials. When the performance of the raw materials cannot meet the actual requirements, the raw materials are modified and then added to achieve the desired function. But in fact, although the aforementioned related research considered the influence of calcium content on the adhesion of oyster larvae, it did not consider the performance of the concrete itself, and did not consider the water-cement ratio, calcium content and curing, etc., and concrete penetration Changes in properties will change the rate of leakage of alkali and ions in concrete. The worse the impermeability of concrete, the greater the rate of leakage of alkali and ions in the concrete, which may be an exponential increase. Therefore, these released alkalis and ions will have a great impact on the larvae, and it may change from promoting adhesion to inhibiting adhesion, especially when the cement content is large, this situation will be more serious. Therefore, adding an inducer to the concrete must ensure that the change in the impermeability of the concrete is within a controllable range, such as the change does not exceed 10%. Only in this way can the induction effects of these be compared. Otherwise, it is impossible to evaluate the effect of single-mixing inducer or compound-mixing inducer on the induction effect of oyster larvae.

只有掌握了海洋固着生物在附着、***及后期生长的所需的最适环境，并能从混凝土的抗渗性高度出发进行设计混凝土，而不是只考虑各种原材料的掺量而忽略由此带来的混凝土的抗渗性改变。因此，同样这部分知识涉及到海洋固着生物、化学与海洋混凝土工程学科的交叉，无论是混凝土及工程领域或者海洋生物领域的技术人员，无法通过现有的背景而获得本发明中的混凝土抗渗性的整体控制与诱导剂促进牡蛎高效诱导附着能力的紧密关联的技术特征。Only by mastering the most suitable environment for the attachment, metamorphosis, and later growth of marine sessile organisms, and designing concrete based on the high degree of impermeability of concrete, instead of only considering the content of various raw materials and ignoring the resultant environment The impermeability of the incoming concrete has changed. Therefore, the same part of the knowledge involves the intersection of marine anchoring biology, chemistry and marine concrete engineering disciplines. Whether it is a person skilled in the field of concrete and engineering or marine biology, it is impossible to obtain the concrete impermeability of the present invention through the existing background. The overall control of sex is closely related to the technical characteristics of the inducer that promotes the ability of oysters to efficiently induce adhesion.

因此，由于这部分知识涉及到海洋固着生物、海洋植物与海洋混凝土工程学科的交叉，无论是混凝土及工程领域或者海洋生物领域的技术人员，无法通过对比文件1-3而获得本发明中的将深色颜料掺入混凝土中改变颜色、牛骨粉改性及粉磨技术和控制混凝土渗透性与具有高效诱导牡蛎附着能力和高耐久性的混凝土紧密关联的技术特征。且无法通过对比文件4而获得本发明中的将混凝土碱度降低与钙离子浓度之间的平衡与海洋固着生物的附着紧密关联的技术特征。Therefore, since this part of knowledge involves the intersection of marine sessile organisms, marine plants and marine concrete engineering disciplines, no matter the technical personnel in the concrete and engineering fields or marine biology fields, they cannot obtain the general principles of the present invention through the reference documents 1-3. Dark pigments are mixed into concrete to change the color, beef bone powder modification and grinding technology, and control of concrete permeability are closely related to the technical characteristics of concrete with high efficiency inducing oyster adhesion and high durability. And it is impossible to obtain the technical feature of the present invention that the balance between the reduction of concrete alkalinity and the calcium ion concentration is closely related to the adhesion of marine sessile organisms through the reference document 4.

实施例A仅用来说明本发明，并不限制本发明的范围。实施例A1～18实施方法相同，而它们的混凝土配合比如下：Example A is only used to illustrate the present invention, and does not limit the scope of the present invention. The implementation methods of Examples A1-18 are the same, and their concrete mixing ratios are as follows:

实施例A1：普通硅酸盐水泥混凝土配合比，普通硅酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：17.1％、46.67％、29.0％、7.2％、0.03％。Example A1: The mixing ratio of ordinary Portland cement concrete, the weight ratios of ordinary Portland cement, crushed stone, sand, water and polycarboxylic acid water reducing agent powder are: 17.1%, 46.67%, 29.0%, 7.2% , 0.03%.

其中所述的碎石的母岩为玄武岩和辉绿岩中一种，其最大粒径不超过50mm，且级配良好；所述的砂为河砂、机制砂(母岩为花岗岩、玄武岩中的一种)或者淡化海砂中的一种或几种，且级配良好。所述的水应符合混凝土用水标准(JGJ63-2006)，Cl ^-含量＜1000mg/L，PH值＞4.5，对水泥初凝时间差及终凝时间、强度及渗透性影响小。且实施例A1～18中所选以上材料相同。 The parent rock of the gravel is one of basalt and diabase, and its maximum particle size is no more than 50mm, and the gradation is good; the sand is river sand, machine-made sand (the parent rock is granite, basalt One) or desalinated one or more of the sea sand, and the gradation is good. The said water should comply with the water standard for concrete (JGJ63-2006), Cl ^- content <1000mg/L, PH value>4.5, and has little effect on the initial setting time difference and final setting time, strength and permeability of cement. And the above materials selected in Examples A1-18 are the same.

实施例A2：基准混凝土配合比，硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：17.1％、46.67％、29.0％、7.2％、0.03％。Example A2: the reference concrete mixing ratio, the weight ratios of sulfoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 17.1%, 46.67%, 29.0%, 7.2%, 0.03%.

通过对比以上实施，可以看出相同掺量的情况下，硫铝酸盐水泥混凝土的电通量更小，说明混凝土具有良好的抗渗性能，同时与普通硅酸盐相比，其牡蛎幼虫附着率显著提高。By comparing the above implementations, it can be seen that under the same dosage, the electric flux of sulphoaluminate cement concrete is smaller, indicating that the concrete has good impermeability performance. At the same time, compared with ordinary silicate, its oyster larvae are attached. The rate has increased significantly.

实施例A3：未改性深色颜料、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、16.59％、46.67％、29.0％、7.2％、0.03％。Example A3: The weight ratio of unmodified dark pigment, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is: 0.51%, 16.59%, 46.67%, 29.0%, 7.2 %, 0.03%.

实施例A4：未改性深色颜料、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、16.24％、46.67％、29.0％、7.2％、0.03％。Example A4: The weight ratio of unmodified dark pigment, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is: 0.86%, 16.24%, 46.67%, 29.0%, 7.2 %, 0.03%.

实施例A5：未改性深色颜料、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、15.73％、46.67％、29.0％、7.2％、0.03％。Example A5: The weight ratio of unmodified dark pigment, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is: 1.37%, 15.73%, 46.67%, 29.0%, 7.2 %, 0.03%.

实施例A6：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、16.59％、46.67％、29.0％、7.2％、0.03％。Example A6: The weight ratio of modified dark pigment (iron oxide black: aniline black mixture mass ratio = 1:1), sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is in order : 0.51%, 16.59%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例A7：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、16.24％、46.67％、29.0％、7.2％、0.03％。Example A7: The weight ratio of modified dark pigment (iron oxide black: aniline black mixture mass ratio = 1:1), sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder is in order : 0.86%, 16.24%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例A8：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、15.73％、46.67％、29.0％、7.2％、0.03％。Example A8: Modified dark pigment (weight ratio of iron oxide black: aniline black mixture = 1:1), sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder in weight ratios are as follows : 1.37%, 15.73%, 46.67%, 29.0%, 7.2%, 0.03%.

改性深色颜料改性方法为：采用196透明树脂，掺加3％的固化剂和1.5％促进剂同颜料混合，且颜料与树脂的体积比为：1:0.2；常温固化4h，60℃固化4h，然后敲碎，用振动磨研磨，细度大于400目即可。The modification method of the modified dark pigment is: adopt 196 transparent resin, mix with 3% curing agent and 1.5% accelerator, and mix with the pigment, and the volume ratio of pigment to resin is 1:0.2; curing at room temperature for 4h, 60℃ Cure for 4 hours, then break it, grind it with a vibration mill, and the fineness is greater than 400 mesh.

黑色颜料对混凝土的渗透性影响很大，并且随着掺量的增加，牡蛎幼虫附着量减少。一方面是由于混凝土渗透性增加，增大了混凝土的碱的渗出，另一方面，可能由于其中的铁氧化物转换为铁离子，导致铁离子浓度增加，会抑制牡蛎幼虫的附着。针对该问题，采用树脂包覆颜料后，再粉磨成粉末，可以大幅度提高混凝土的抗渗性，特别是掺量为1.37％时，其电通量仅增加2.5％。同时随着深色颜料的增加，牡蛎附着持续增加，不同于改性前在掺量为1.37％，表现为牡蛎幼虫附着率下降。The black pigment has a great influence on the permeability of concrete, and with the increase of the content, the attachment of oyster larvae decreases. On the one hand, due to the increase in concrete permeability, the alkali exudation of the concrete is increased. On the other hand, the iron oxides in the concrete may be converted into iron ions, resulting in an increase in the concentration of iron ions, which will inhibit the attachment of oyster larvae. In view of this problem, the resin is coated with the pigment and then ground into powder, which can greatly improve the impermeability of the concrete, especially when the content is 1.37%, the electric flux is only increased by 2.5%. At the same time, with the increase of dark pigments, the attachment of oysters continued to increase, which was different from the 1.37% content before modification, which showed that the attachment rate of oyster larvae decreased.

实施例A9：未改性牛骨粉、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、16.59％、46.67％、29.0％、7.2％、0.03％。Example A9: The weight ratios of unmodified bovine bone powder, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 0.51%, 16.59%, 46.67%, 29.0%, 7.2% , 0.03%.

实施例A10：未改性牛骨粉、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、16.24％、46.67％、29.0％、7.2％、0.03％。Example A10: The weight ratios of unmodified bovine bone powder, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water reducing agent powder are: 0.86%, 16.24%, 46.67%, 29.0%, 7.2% , 0.03%.

实施例A11：未改性牛骨粉、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、15.73％、46.67％、29.0％、7.2％、0.03％。Example A11: The weight ratios of unmodified bovine bone powder, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 1.37%, 15.73%, 46.67%, 29.0%, 7.2%. , 0.03%.

实施例A12：改性牛骨粉、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.51％、16.59％、46.67％、29.0％、7.2％、0.03％。Example A12: The weight ratios of modified bovine bone powder, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 0.51%, 16.59%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例A13：改性牛骨粉、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：0.86％、16.24％、46.67％、29.0％、7.2％、0.03％。Example A13: The weight ratios of modified bovine bone powder, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water-reducing agent powder are: 0.86%, 16.24%, 46.67%, 29.0%, 7.2%, 0.03%.

实施例A14：改性牛骨粉、硫铝酸盐水泥、碎石、砂、水和聚羧酸减水剂粉重量配比依次为：1.37％、15.73％、46.67％、29.0％、7.2％、0.03％。Example A14: The weight ratios of modified bovine bone powder, sulphoaluminate cement, crushed stone, sand, water and polycarboxylic acid water reducer powder are: 1.37%, 15.73%, 46.67%, 29.0%, 7.2%, 0.03%.

牛骨粉改性方法为：将100目的牛骨粉加入到浓度2％的磷酸溶液，两者的重量比为1:3，温度为20～30℃，在转速为200～500转/分搅拌器内搅拌30分钟，采用3000～5000转/分的离心机离心3分钟，倒掉上清液，并用水清洗离心后的固体物质的固体物质2～3次，洗涤水不再显示酸性；将离心后的固体物质在40℃真空干燥，将干燥的牛骨粉与矿渣粉1:4混合，用振动磨粉磨到细度大于200目，待用。The modification method of beef bone meal is: adding 100 mesh beef bone meal to a 2% phosphoric acid solution, the weight ratio of the two is 1:3, the temperature is 20-30℃, and the rotating speed is 200-500 rpm in a stirrer Stir for 30 minutes, centrifuge at 3000-5000 rpm for 3 minutes, discard the supernatant, and wash the solid matter after centrifugation with water for 2 to 3 times, the washing water no longer shows acidity; after centrifugation The solid material is dried in vacuum at 40°C, and the dried beef bone powder and slag powder are mixed 1:4, and ground to a fineness of more than 200 mesh with a vibrating mill, and set aside.

实施例A15：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、硫铝酸盐水泥、碎石、砂、水、碳酸钠和聚羧酸减水剂粉重量配比依次为：0.86％、15.94％、46.67％、29.0％、7.2％、0.3％、0.03％。Example A15: Modified dark pigment (weight ratio of iron oxide black: aniline black mixture = 1:1), sulphoaluminate cement, crushed stone, sand, water, sodium carbonate and polycarboxylic acid water reducer powder The ratios are: 0.86%, 15.94%, 46.67%, 29.0%, 7.2%, 0.3%, 0.03%.

实施例A16：改性深色颜料(氧化铁黑:苯胺黑混合物质量比＝1:1)、硫铝酸盐水泥、碎石、砂、水、碳酸钠和聚羧酸减水剂粉重量配比依次为：0.86％、15.44％、46.67％、29.0％、7.2％、0.8％、0.03％。Example A16: Modified dark pigment (weight ratio of iron oxide black: aniline black mixture = 1:1), sulfoaluminate cement, crushed stone, sand, water, sodium carbonate and polycarboxylic acid water reducer powder The ratios are: 0.86%, 15.44%, 46.67%, 29.0%, 7.2%, 0.8%, 0.03%.

碳酸钠改性方法为：选取硅藻土SiO ₂含量＞90％，细度600目的硅藻土，常温下，将100g碳酸钠加入到100g水中，搅拌到溶解完全，待用；然后采用将150g上述的硅藻土添加到溶液中，转速为200～500转/分搅拌器内搅拌30分钟，然后在烘干温度为100℃的干燥箱中干燥，即得产品。 The modification method of sodium carbonate is: select diatomaceous earth with SiO ₂ content> 90% and fineness of 600 mesh diatomaceous earth, add 100 g of sodium carbonate to 100 g of water at room temperature, stir until it is completely dissolved, and set aside; then use 150 g of diatomaceous earth The above-mentioned diatomaceous earth is added to the solution, stirred in a stirrer with a rotation speed of 200-500 rpm for 30 minutes, and then dried in a drying oven at a drying temperature of 100° C. to obtain the product.

本实例通过复合掺加深色颜料、碳酸钠来提供深色的混凝土表面，满足牡蛎眼点幼虫的避光要求，以及提供牡蛎幼虫附着、***时所需的碳酸钙的合成，复合掺加可以提升牡蛎幼虫的附着率，当深色颜料比例为0.86％和碳酸钠的比例为0.8％时，其附着率提升了116％。证明了碳酸钠可以促进牡蛎幼虫的诱导附着。In this example, a dark concrete surface is provided by compounding with dark pigments and sodium carbonate, which meets the light-proof requirement of oyster larvae, and provides the synthesis of calcium carbonate required for attachment and metamorphosis of oyster larvae. The compound addition can improve The adhesion rate of oyster larvae was increased by 116% when the proportion of dark pigment was 0.86% and the proportion of sodium carbonate was 0.8%. It is proved that sodium carbonate can promote the induction of the attachment of oyster larvae.

实施例A17：改性深色颜料、硫铝酸盐水泥、碎石、砂、水、生物碳酸钙颗粒、碳酸钠和聚羧酸减水剂粉重量配比依次为：0.86％、15.44％、46.67％、19.3％、7.2％、9.7％、0.8％、0.03％。Example A17: The weight ratio of modified dark pigment, sulphoaluminate cement, crushed stone, sand, water, biological calcium carbonate particles, sodium carbonate and polycarboxylic acid water-reducing agent powder is 0.86%, 15.44%, 46.67%, 19.3%, 7.2%, 9.7%, 0.8%, 0.03%.

实施例A18：改性深色颜料、硫铝酸盐水泥、生物钙粉、碎石、砂、水、生物碳酸钙颗粒、碳酸钠和聚羧酸减水剂粉重量配比依次为：0.86％、14.58％、0.86％、46.67％、19.3％、7.2％、9.7％、0.8％、0.03％。Example A18: The weight ratio of modified dark pigment, sulphoaluminate cement, biological calcium powder, crushed stone, sand, water, biological calcium carbonate particles, sodium carbonate and polycarboxylic acid water-reducing agent powder is in order: 0.86% , 14.58%, 0.86%, 46.67%, 19.3%, 7.2%, 9.7%, 0.8%, 0.03%.

本实例通过采用生物碳酸钙颗粒(牡蛎壳碎)替代砂质量的30％，由于牡蛎壳是一种废弃资源，利用率低，且目前将其作为垃圾的处理方法对环境污染严重。因此，本实例将其以合适的配比掺入混凝土中，在保证混凝土基本性能无显著影响的前提下，既可以为牡蛎幼虫的附着***发育提供一定的营养物质，又实现了废弃资源的二次利用，达到了诱导海洋固着生物附着的绿色混凝土预期的节能、环保的效果。In this example, biological calcium carbonate particles (crushed oyster shells) are used to replace 30% of the quality of the sand. Because oyster shells are a waste resource, the utilization rate is low, and the current waste disposal method has serious environmental pollution. Therefore, in this example, it was mixed into concrete at an appropriate ratio. Under the premise of ensuring that the basic performance of concrete is not significantly affected, it can not only provide certain nutrients for the attachment and metamorphosis of oyster larvae, but also realize the second use of waste resources. The second use achieves the expected energy-saving and environmental-friendly effects of green concrete that induces the attachment of marine sessile organisms.

实施例A1～18实施方法具体操作步骤如下：The specific operation steps of the implementation methods of Examples A1-18 are as follows:

按照上述的一种诱导海洋固着生物附着的绿色混凝土的制备方法，制备3个Φ100×50mm圆柱体试件和10块200×200×30mm长方体试件，分别用于测试该混凝土标准养护的28d抗氯离子渗透性和标准养护28d后实验室内牡蛎幼虫附着***情况。具体操作步骤如下：According to the above-mentioned preparation method of green concrete that induces the adhesion of marine fixed organisms, 3 Φ100×50mm cylindrical specimens and 10 200×200×30mm cuboid specimens were prepared to test the 28d resistance of the concrete under standard curing. Chloride ion permeability and oyster larvae attachment metamorphosis in the laboratory after 28 days of standard curing. The specific steps are as follows:

(一)试件成型(1) Specimen molding

1、计算并按照上述的质量精确称量硫铝酸盐水泥、碎石、砂、水、深色颜料、生物钙粉、生物碳酸钙颗粒、碳酸钠和聚羧酸减水剂粉。1. Calculate and accurately weigh the sulfoaluminate cement, gravel, sand, water, dark pigment, biological calcium powder, biological calcium carbonate particles, sodium carbonate and polycarboxylic acid water reducer powder according to the above-mentioned mass.

2、先将碎石、砂和生物碳酸钙颗粒放入混凝土搅拌机中搅拌0.5～1分钟；然后加入硫铝酸盐水泥、生物钙粉、碳酸钠、深色颜料，再继续搅拌0.5～1分钟；然后加入水和超塑化剂搅拌2～6分钟；搅拌均匀后，进行浇筑、振捣、拆模，即可制得3个Φ100×50mm圆柱体试件和10块200×200×30mm长方体试件；最后将其放入标准养护室持续28d，并在28d进行相应的渗透性能评价，以及在28d后进行实验室内牡蛎幼虫附着、***实验。2. Put the gravel, sand and biological calcium carbonate particles into the concrete mixer and mix for 0.5 to 1 minute; then add sulphoaluminate cement, biological calcium powder, sodium carbonate, and dark pigments, and continue to mix for 0.5 to 1 minute ; Then add water and superplasticizer and stir for 2-6 minutes; after stirring evenly, pour, vibrate, and remove the mold, you can get 3 Φ100×50mm cylindrical specimens and 10 200×200×30mm cuboids Specimen; finally put it into the standard curing room for 28 days, and perform the corresponding permeability evaluation on 28 days, and perform the oyster larva attachment and metamorphosis experiments in the laboratory after 28 days.

标准养护28d后，分别从养护室中取出200×200×30mm长方体试件，并将其表面水分及杂物清理干净，随后放入试验池中，并且实验室内准备试验池，牡蛎幼虫丰度为0.85ind/ml ³，池中海水为砂滤后的黄海海水，盐度约为32％～34％，待海水水位高于混凝土试件后，将氧气管均匀散布在试验池中，准备牡蛎幼虫投放。将牡蛎幼虫在水桶中缓慢搅拌均匀后，使用烧杯准确称量含有牡蛎幼虫的海水质量，接着将其均匀分布于试验池中。并在诱导牡蛎附着试验开始后，将试验池内海水每日进行更换，换水量为试验池总容量的1/3，使用筛网(≥200目)堵在排水口，防止未附着的牡蛎幼苗随水流失，将筛网上的幼苗再次投放到试验池中，之后每日9时及19时使用胶头滴管定时定量投喂小球藻，并观察牡蛎附着情况。试验持续30d后，将试验池中的水排出，取出试件，对试件表面牡蛎数目及成活率进行统计记录分析，统计时取混凝土浇筑成型时光滑的底面。 After 28 days of standard curing, take out the 200×200×30mm cuboid specimens from the curing room, clean the surface water and debris, and then put them in the test pool, and prepare the test pool in the laboratory. The abundance of oyster larvae It is 0.85ind/ml ³ , the seawater in the pond is the Yellow Sea seawater after sand filtration, and the salinity is about 32% to 34%. After the seawater level is higher than the concrete specimen, the oxygen pipes are evenly distributed in the test pond to prepare oysters Larvae are released. After slowly stirring the oyster larvae in a bucket, use a beaker to accurately weigh the quality of the seawater containing the oyster larvae, and then distribute them evenly in the test tank. And after the start of the oyster attachment test, the seawater in the test pool was replaced daily, and the amount of water changed was 1/3 of the total capacity of the test pool. A screen (≥200 mesh) was used to block the drain to prevent unattached oyster seedlings from following. After the water was lost, the seedlings on the sieve were put into the test pond again, and then the chlorella was regularly and quantitatively fed with a rubber-tip dropper at 9 o'clock and 19 o'clock every day, and the attachment of oysters was observed. After the test lasts for 30 days, drain the water in the test pool, take out the test piece, and analyze the number of oysters on the surface of the test piece and the survival rate. The statistics take the smooth bottom surface when the concrete is poured.

本发明与对比文件1(一种新型混凝土人工鱼礁及其制备方法CN104529286 A)相比，区别在于：Compared with Comparative Document 1 (a new type of concrete artificial reef and its preparation method CN104529286 A), the difference between the present invention is:

与对比文件2(一种仿生混凝土人工鱼礁及其制备方法2015CN104938384 A)相比，区别在于：Compared with comparative document 2 (a bionic concrete artificial reef and its preparation method 2015CN104938384 A), the difference is:

(1)本发明中的目的与对比文件2不同。对比文件2虽然在混凝土中掺加牡蛎壳或牡蛎壳粉，但它的目的主要通过表面的仿生性来实现，集鱼、集微生物、藻类，增加微生物数量改善水体环境，未提及牡蛎。而本发明的目的是诱导固着生物附着，主要为牡蛎，在潮差区钢筋混凝土防腐蚀时，考虑藤壶的附着。(1) The purpose of the present invention is different from that of Reference Document 2. In Comparative Document 2, although the concrete is mixed with oyster shell or oyster shell powder, its purpose is mainly realized by the surface bionics, collecting fish, microorganisms, and algae, increasing the number of microorganisms and improving the water environment. No mention of oysters. The purpose of the present invention is to induce the attachment of sessile organisms, mainly oysters, and the attachment of barnacles is considered when the reinforced concrete is anti-corrosive in the tidal range.

(3)通过对牛骨粉和生物碳酸钙粉的改性，具体为对100目到500目间的鸡蛋壳粉、珊瑚粉、牡蛎壳粉、鱼骨粉采用弱酸进行处理，包括乙酸、醋酸、硅酸、亚硫酸等中的一种或两种；对100目到500目牛骨粉，采用稀释的磷酸、硫酸、盐酸和硝酸中的一种或两种。(3) Through the modification of bovine bone meal and biological calcium carbonate powder, specifically the egg shell powder, coral powder, oyster shell powder, and fish bone powder between 100 mesh and 500 mesh are treated with weak acids, including acetic acid, acetic acid, and silicon. One or two of acid, sulfurous acid, etc.; for 100 mesh to 500 mesh beef bone meal, use one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

(3)由于牛骨粉中含有丰富的胶原蛋白等有机物质，这些物质的大量掺入会引起混凝土强度和抗渗性下降，特别是超过5％后，增大掺量，混凝土强度迅速下降、抗渗性显著变差，以及标准养护条件下混凝土表面会长霉。(3) Because bovine bone meal is rich in organic substances such as collagen, a large amount of these substances will cause the strength and impermeability of concrete to decrease, especially if it exceeds 5%, increase the amount of concrete, and the strength of concrete will decrease rapidly. The permeability is significantly worse, and the surface of the concrete will grow mildew under standard curing conditions.

本发明通过控制采用稀酸改性和复合粉磨技术，充分发挥牛骨粉的诱导能力，大幅度降低牛骨粉掺量，并进行防腐蚀处理及改性，实现了以牛骨粉为主的复合诱导剂，其掺量小，几乎不影响混凝土强度和渗透性，同时具有很强的牡蛎幼虫附着能力，且解决了混凝土的发霉问题。相对于不掺加诱导剂的混凝土，掺加诱导剂的混凝土牡蛎幼虫附着个数明显增加。By controlling the use of dilute acid modification and composite grinding technology, the present invention gives full play to the inducing ability of bovine bone powder, greatly reduces the amount of bovine bone powder, and carries out anti-corrosion treatment and modification, and realizes the compound induction based on bovine bone powder. It has a small content and hardly affects the strength and permeability of concrete. At the same time, it has strong adhesion of oyster larvae, and solves the problem of mildew in concrete. Compared with the concrete without the inducer, the number of oyster larvae on the concrete with the inducer increased significantly.

对比文件及查阅到的文献资料表明：钙含量对牡蛎幼虫的附着至关重要，同样目前一些实验结果也证明在水泥基材料中掺加适量的碳酸钙质的物质可以促进牡蛎幼虫的附着及生长。但是水泥混凝土中有大量的钙离子，孔溶液中的pH值一般大于12.5，饱和氢氧化钙溶液的pH值在常温约为12，所以混凝土孔溶液中的钙离子浓度约5mmol/L；而碳酸钙的溶解度很小，在25℃时只有9.5×10 ^-5mol/L(9.5×10 ^-2mmol/L)。目前认为诱导牡蛎附着的钙离子浓度最佳范围为10～25mmol/L，即使将牡蛎幼虫放置在饱和的碳酸钙溶液中，也没有足够的Ca ²⁺浓度为牡蛎附着提供适宜的离子浓度。进一步说，水泥混凝土内部的Ca(OH) ₂可以较快的释放出来，而碳酸钙的溶解则需要较长的时间。因此，可以确定在混凝土中掺入碳酸钙质材料促进牡蛎幼虫的附着，Ca ²⁺不是起主导作用。牡蛎的早期附着、***与HCO ₃ ^-有关，在***时和Ca ²⁺一起生成碳酸钙的次生壳。掺加碳酸钙后，由于碳酸钙与CO ₂和水反应，生成Ca(HCO ₃) ₂后参与附着，是其对牡蛎幼虫附着促进的根本机理。 The comparative documents and the literature data that have been consulted show that the calcium content is very important for the attachment of oyster larvae. Similarly, some current experimental results also prove that adding an appropriate amount of calcium carbonate to cement-based materials can promote the attachment and growth of oyster larvae. . However, there are a lot of calcium ions in cement concrete. The pH value in the pore solution is generally greater than 12.5. The pH value of the saturated calcium hydroxide solution is about 12 at room temperature, so the calcium ion concentration in the concrete pore solution is about 5mmol/L; The solubility of calcium is very small, only 9.5×10 ^-5 mol/L (9.5×10 ^-2 mmol/L) at 25°C. At present, it is believed that the best range of calcium ion concentration for inducing oyster attachment is 10-25mmol/L. Even if oyster larvae are placed in a saturated calcium carbonate solution, there is not enough Ca ²⁺ concentration to provide a suitable ion concentration for oyster attachment. Furthermore, the Ca(OH) ₂ inside the cement concrete can be released relatively quickly, while the dissolution of calcium carbonate takes a longer time. Therefore, it can be determined that calcium carbonate is added to concrete to promote the attachment of oyster larvae, and Ca ²⁺ does not play a leading role. The early attachment and metamorphosis of oysters are related to HCO ₃ ^- , and ^{together with Ca 2+,} they form secondary shells of calcium carbonate. After adding calcium carbonate, the calcium carbonate _{reacts with CO 2} and water to form Ca(HCO ₃ ) ₂ and participate in the attachment, which is the fundamental mechanism for promoting the attachment of oyster larvae.

采用低碱度的硫铝酸盐水泥的复合，调控水泥混凝土的碱度，为牡蛎幼虫附着提供适宜的pH值。此外，海洋植物和牡蛎、藤壶等固着生物耐碱能力不同，且在附着期及后期需要的环境不同，如藤壶和牡蛎的附着、***及后期生长都需要大量的钙离子。以及由于硫铝酸盐水泥的碱度低，并且快硬硫铝酸盐水泥、高强硫铝酸盐水泥、膨胀硫铝酸盐的碱度不同，可以根据实际所需的碱度进行复合掺加，可以给牡蛎和藤壶幼虫在其表面附着提供适宜的碱度。同时硫铝酸盐水泥具有早强、高强的特点，可以实现工程的快速建造，同时具有高的抗渗性能和耐腐蚀性，特别是具有高的抗硫酸盐腐蚀的性能，在海洋工程以及需快速修补工程中具有显著的优势。The compound of low alkalinity sulphoaluminate cement is used to control the alkalinity of cement concrete and provide a suitable pH value for the attachment of oyster larvae. In addition, marine plants and oysters, barnacles and other sessile organisms have different alkali resistance capabilities, and require different environments during the attachment period and later period. For example, barnacles and oysters require a large amount of calcium ions for attachment, metamorphosis, and late growth. And because the alkalinity of sulphoaluminate cement is low, and the alkalinity of fast hardening sulphoaluminate cement, high-strength sulphoaluminate cement, and expanded sulphoaluminate cement is different, it can be compounded according to the actual alkalinity required. , Can provide suitable alkalinity for oysters and barnacle larvae to attach on their surface. At the same time, sulfoaluminate cement has the characteristics of early strength and high strength, which can realize the rapid construction of the project, and at the same time has high impermeability and corrosion resistance, especially high sulfate corrosion resistance. It is used in marine engineering and demand It has significant advantages in rapid repair engineering.

颜色：colour:

碳酸(氢)盐：Bicarbonates:

根据发明人研究得到的在水泥基材料中掺加碳酸钙质物质诱导牡蛎附着的主要作用机理是其中的CO ₃ ^2-对牡蛎幼虫附着、***起主要作用，而不是Ca ²⁺起主导作用，所以本发明中创新性地提出采用非碳酸钙的碳酸盐，碳酸氢盐进行牡蛎幼虫在混凝土表面的诱导附着。因此，采用碳酸(氢)盐(碳酸钠、碳酸钾，碳酸氢钙、碳酸氢钠、碳酸氢钾等)掺入混凝土中，并通过改性，使混凝土的强度和抗渗性基本保持不变，实现牡蛎幼虫诱导附着率大幅度增加。具体为： According to the inventor’s research, the main mechanism of adding calcium carbonate to cement-based materials to induce oyster attachment is that CO ₃ ^2- plays a major role in the attachment and metamorphosis of oyster larvae, rather than Ca ²⁺ . Therefore, the present invention innovatively proposes to use non-calcium carbonate carbonate and bicarbonate to induce the attachment of oyster larvae on the concrete surface. Therefore, using carbonate (bi) salt (sodium carbonate, potassium carbonate, calcium bicarbonate, sodium bicarbonate, potassium bicarbonate, etc.) into concrete, and through modification, the strength and impermeability of concrete remain basically unchanged , To achieve a substantial increase in the induced attachment rate of oyster larvae. Specifically:

海洋生物研究人员，为了明晰牡蛎附着机理及养殖增殖的目的，研究不同的离子对海洋固着生物的附着、***研究，属于海洋生物学科。和海洋混凝土工程或者混凝土材料学科相差较大，完全是两个大的学科。通过海洋固着生物与混凝土学科的交叉，得到了在混凝土中加入相应的物质，来诱导牡蛎幼虫在混凝土表面的附着。因可溶性盐类对混凝土的性能影响很大，如影响早期的工作性、凝结时间以及后期的强度与抗渗性，本发明通过采用硅藻土为载体，把这些盐类固定在硅藻土的内部，减小可溶性盐对混凝土的性能影响，同时利用硅藻土对混凝土性能提升的作用，实现在掺加这些诱导物质时，仍可以保持混凝土的良好力学性能和抗渗性能。另外由于硅藻土作为载体具有缓释作用，使可溶性盐释放较缓慢，特别是经过海水浸泡超过一定时间后，释放速率维持在一个很小的速率。因此，同样这部分知识涉及到海洋固着生物、化学与海洋混凝土工程学科的交叉，无论是混凝土及工程领域或者海洋生物领域的技术人员，无法通过现有的背景而获得本发明中的将碳酸(氢)盐掺入混凝土，改变混凝土表面的碳酸(氢)根的含量和控制混凝土渗透性与具有高诱导牡蛎附着能力的混凝土紧密关联的技术特征。Marine biological researchers, in order to clarify the attachment mechanism of oysters and the purpose of breeding and proliferation, study the attachment and metamorphosis of different ions to marine sessile organisms, belonging to the Department of Marine Biology. It is quite different from marine concrete engineering or concrete materials disciplines, and they are completely two major disciplines. Through the intersection of marine fixed organisms and concrete disciplines, it was obtained that the corresponding substances were added to the concrete to induce the attachment of oyster larvae on the concrete surface. Because soluble salts have a great influence on the performance of concrete, such as affecting early workability, setting time, and later strength and impermeability, the present invention uses diatomaceous earth as a carrier to fix these salts on the diatomaceous earth. Internally, it reduces the influence of soluble salts on the performance of concrete, and at the same time uses the effect of diatomaceous earth on the performance of concrete to realize that when these inducing substances are added, the good mechanical properties and impermeability of concrete can still be maintained. In addition, because diatomaceous earth has a slow-release effect as a carrier, the release of soluble salts is relatively slow, especially after being soaked in seawater for a certain period of time, the release rate is maintained at a very small rate. Therefore, this same part of knowledge involves the intersection of marine sessile biology, chemistry and marine concrete engineering disciplines. Whether it is a person skilled in the field of concrete and engineering or marine biology, it is impossible to obtain the carbonic acid in the present invention through the existing background ( Hydrogen) salt is mixed into concrete to change the content of carbonic acid (bicarbonate) on the surface of concrete and control the permeability of concrete. The technical characteristics are closely related to concrete with high ability to induce oyster adhesion.

混凝土渗透性：Concrete permeability:

混凝土的强度和渗透性是混凝土最主要的两个性能。而在基准混凝土中掺加不同的诱导剂，都会对混凝土性能产生影响，因此，在考虑掺加不同物质促进牡蛎幼虫附着、***及后期生长时，首先一定要从整体控制其对混凝土的强度和渗透性不产生大的影响，然后再根据各种原材料的配伍性去选择原材料，当原材料性能不能满足实际要求时，则通过对原材料的改性后再加入，从而达到预期效果。但实际上，前述的相关研究虽然考虑到了钙质的掺量对牡蛎幼虫附着的影响，但是不考虑混凝土本身的性能，不去考虑水灰比以及钙质的掺量以及养护等，而混凝土渗透性的变化会使混凝土内部碱和离子渗漏的速率改变，混凝土的抗渗性越差，其内部的碱和离子的渗漏速率越大，可能以指数形式增长。因此，这些释放出来的碱和离子会对幼虫产生很大影响，可能出现从促进附着变为抑制附着的情况，特别水泥掺量大时，这种情况会更严重。因此，混凝土中掺加诱导剂，一定要保证混凝土的抗渗性的变化在可控的范围内，如变化不超过10％。这样才能对这些诱导效果进行比较，否则的话，则无法评价单掺诱导剂或者诱导剂复合掺加对牡蛎幼虫诱导效果的影响。The strength and permeability of concrete are the two most important properties of concrete. The addition of different inducers to the benchmark concrete will have an impact on the performance of the concrete. Therefore, when considering the addition of different substances to promote the attachment, metamorphosis and later growth of the oyster larvae, the overall strength and strength of the concrete must be controlled first. The permeability does not have a big impact, and then the raw materials are selected according to the compatibility of various raw materials. When the properties of the raw materials cannot meet the actual requirements, the raw materials are modified and then added to achieve the desired effect. But in fact, although the aforementioned related research considered the influence of calcium content on the adhesion of oyster larvae, it did not consider the performance of the concrete itself, and did not consider the water-cement ratio, calcium content and curing, etc., and concrete penetration Changes in properties will change the rate of alkali and ion leakage in concrete. The worse the impermeability of concrete, the greater the rate of leakage of alkali and ions in the concrete, which may increase exponentially. Therefore, these released alkalis and ions will have a great impact on the larvae, and it may change from promoting adhesion to inhibiting adhesion, especially when the cement content is large, this situation will be more serious. Therefore, adding an inducer to the concrete must ensure that the change in the impermeability of the concrete is within a controllable range, such as the change does not exceed 10%. Only in this way can these induction effects be compared. Otherwise, it is impossible to evaluate the effect of single or compound inducing agent on the induction effect of oyster larvae.

因此，由于这部分知识涉及到海洋固着生物、海洋植物与海洋混凝土工程学科的交叉，无论是混凝土及工程领域或者海洋生物领域的技术人员，无法通过对比文件1-3而获得本发明中的将深色颜料掺入混凝土中改变颜色、生物钙粉改性及粉磨技术以及掺入改性的碳酸盐和控制混凝土渗透性与具有高效诱导牡蛎附着能力和高耐久性的混凝土紧密关联的技术特征。Therefore, since this part of knowledge involves the intersection of marine sessile organisms, marine plants and marine concrete engineering disciplines, no matter the technical personnel in the concrete and engineering fields or marine biology fields, they cannot obtain the general principles of the present invention through the reference documents 1-3. Dark pigments are mixed into concrete to change the color, bio-calcium powder modification and grinding technology, and the mixing of modified carbonates and the control of concrete permeability are closely related to the concrete with high efficiency in inducing oyster adhesion and high durability. feature.

尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. And variations, the scope of the present invention is defined by the appended claims and their equivalents.

Claims

一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：由包括硅酸盐水泥、矿物掺合料、碎石、砂、水、深色颜料、生物钙粉和超塑化剂制成，硅酸盐水泥、矿物掺合料、碎石、砂、水、深色颜料、生物钙粉和超塑化剂重量配比依次为：8.5％～16.0％、3.5％～11.0％、39.4％～49.8％、24.9％～37.3％、6.2％～8.7％、0.2％～1.7％、0.2～1.7％和0.02％～0.1％。A dark Portland cement concrete that induces the attachment of marine sessile organisms, which is characterized in that it is composed of Portland cement, mineral admixtures, gravel, sand, water, dark pigments, biological calcium powder and superplasticizing The weight ratio of Portland cement, mineral admixture, crushed stone, sand, water, dark pigment, biological calcium powder and superplasticizer is 8.5%-16.0%, 3.5%-11.0% , 39.4%～49.8%, 24.9%～37.3%, 6.2%～8.7%, 0.2%～1.7%, 0.2～1.7% and 0.02%～0.1%.
根据权利要求1所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：所述深色颜料为氧化铁黑、苯胺黑、炭黑、硫化锑、氧化铁红、有机颜料红中的一种或两种。The dark Portland cement concrete for inducing the adhesion of marine sessile organisms according to claim 1, wherein the dark pigment is iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red, One or two of organic pigment red.
根据权利要求2所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：所述的深色颜料根据对混凝土的性能影响程度，进行这些颜料的改性，采用透明树脂、有机硅、二甲硅氧烷、超疏水材料中的一种进行改性处理。The dark Portland cement concrete for inducing the adhesion of marine sessile organisms according to claim 2, characterized in that: the dark pigments are modified according to the degree of influence on the performance of the concrete, using transparent One of resin, silicone, dimethylsiloxane, and superhydrophobic material is modified.
根据权利要求1所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：所述的生物钙粉为牛骨粉和生物碳酸钙粉包括牡蛎壳粉、鱼骨粉、鸡蛋壳粉、珊瑚粉中的一种或几种复合，其细度为100目～1000目。The dark Portland cement concrete for inducing the attachment of marine sessile organisms according to claim 1, wherein the biological calcium powder is bovine bone powder and biological calcium carbonate powder including oyster shell powder, fish bone powder, and egg One or a combination of shell powder and coral powder, with a fineness of 100 mesh to 1000 mesh.
根据权利要求4所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：所述的生物钙粉，对100目到500目间的牡蛎壳粉、鸡蛋壳粉、珊瑚粉、鱼骨粉采用以下酸进行处理，包括乙酸、醋酸、硅酸、亚硫酸中的一种或两种；以及对100目到500目牛骨粉采用以下酸进行处理，包括稀释的磷酸、硫酸、盐酸和硝酸中的一种或两种。The dark Portland cement concrete for inducing the attachment of marine sessile organisms according to claim 4, characterized in that: the biological calcium powder is suitable for oyster shell powder, egg shell powder, and egg shell powder between 100 mesh and 500 mesh. Coral meal and fish bone meal are treated with the following acids, including one or two of acetic acid, acetic acid, silicic acid, and sulfurous acid; and for cattle bone meal from 100 mesh to 500 mesh, the following acids are used for treatment, including diluted phosphoric acid and sulfuric acid , One or two of hydrochloric acid and nitric acid.
根据权利要求1所述的所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：所述的硅酸盐水泥为普通硅酸盐水泥，强度等级＞32.5，所述的矿物掺合料包括硅灰、矿渣粉和粉煤灰中的一种或多种组合。The dark Portland cement concrete for inducing the attachment of marine sessile organisms according to claim 1, characterized in that: the Portland cement is ordinary Portland cement with a strength grade> 32.5, so The said mineral admixture includes one or more combinations of silica fume, slag powder and fly ash.
根据权利要求1所述的所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：所述的砂为河砂、机制砂或者淡化海砂中的一种或几种。The dark Portland cement concrete for inducing the attachment of marine sessile organisms according to claim 1, wherein the sand is one or more of river sand, machine-made sand or desalinated sea sand. Kind.
一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土的制备方法，其特征在于，包括如下步骤：A preparation method of dark Portland cement concrete for inducing the attachment of marine sessile organisms, which is characterized in that it comprises the following steps:

S1：精确称量硅酸盐水泥、矿物掺合料、碎石、砂、水、深色颜料、生物钙粉和超塑化剂；S1: Accurately weigh Portland cement, mineral admixtures, gravel, sand, water, dark pigments, biological calcium powder and superplasticizer;

S2：先将碎石和砂放入混凝土搅拌机中搅拌0.5～1分钟；然后加入硅酸盐水泥、矿物掺合料、生物钙粉、深色颜料，再继续搅拌0.5～1分钟；然后加入水和超塑化剂搅拌2～6分钟；搅拌均匀后，进行浇筑、振捣，随后进行标准养护28d或根据实际情况进行养护，即一种可制得诱导效果良好的海洋固着生物附着的深色硅酸盐水泥混凝土。S2: Put the gravel and sand into the concrete mixer and mix for 0.5 to 1 minute; then add Portland cement, mineral admixtures, biological calcium powder, and dark pigments, and continue to mix for 0.5 to 1 minute; then add water Stir with superplasticizer for 2 to 6 minutes; after stirring evenly, pour, vibrate, and then carry out standard curing for 28 days or curing according to the actual situation, that is, a dark color that can produce a good inducing effect of marine fixed organisms adhesion Portland cement concrete.
根据权利要求1所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：由包括深色颜料、胶凝材料、碎石、砂、水和超塑化剂制成，深色颜料、胶凝材料、碎石、砂、水和超塑化剂粉重量配比依次为：0.2％～1.7％、12.5％～22.0％、39.4％～49.8％、24.9％～37.3％、6.2％～8.7％、0.02％～0.1％。The dark Portland cement concrete for inducing the attachment of marine sessile organisms according to claim 1, characterized in that it is made of dark pigments, cementing materials, gravel, sand, water and superplasticizers , The weight ratio of dark pigment, gelling material, crushed stone, sand, water and superplasticizer powder are: 0.2%～1.7%, 12.5%～22.0%, 39.4%～49.8%, 24.9%～37.3% , 6.2% to 8.7%, 0.02% to 0.1%.
根据权利要求1所述的一种诱导海洋固着生物附着的深色硅酸盐水泥混凝土，其特征是：由包括生物钙粉、胶凝材料、碎石、砂、水和超塑化剂制成，生物钙粉、胶凝材料、碎石、砂、水和超塑化剂重量配比依次为：0.2％～1.7％、12.5％～22.0％、39.4％～49.8％、24.9％～37.3％、6.2％～8.7％、0.02％～0.1％。The dark Portland cement concrete for inducing the attachment of marine sessile organisms according to claim 1, characterized in that it is made of bio-calcium powder, cementitious material, gravel, sand, water and superplasticizer , The weight ratio of bio-calcium powder, cementitious material, crushed stone, sand, water and superplasticizer are: 0.2%～1.7%, 12.5%～22.0%, 39.4%～49.8%, 24.9%～37.3%, 6.2%～8.7%, 0.02%～0.1%.
一种诱导海洋固着生物附着的绿色混凝土，其特征是：由包括胶凝材料、碎石、砂、水、深色颜料、生物钙粉、生物碳酸钙颗粒、碳酸盐或碳酸氢盐和超塑化剂制成，胶凝材料、碎石、砂、水、深色颜料、生物钙粉、生物碳酸钙颗粒、碳酸盐或碳酸氢盐和超塑化剂重量配比依次为：13.3％～22.8％、 39.4％～49.8％、0％～24.6％、6.2％～8.7％、0.2％～1.7％、0.2～1.7％、8.0％～33.5％、0.2～1.7％和0.02％～0.1％。A green concrete that induces the attachment of marine fixed organisms, which is characterized by: it is made of cementitious materials, gravel, sand, water, dark pigments, biological calcium powder, biological calcium carbonate particles, carbonate or bicarbonate and super Made of plasticizer, the weight ratio of gelling material, gravel, sand, water, dark pigment, biological calcium powder, biological calcium carbonate particles, carbonate or bicarbonate and superplasticizer is 13.3% ～22.8%, 39.4%～49.8%, 0%～24.6%, 6.2%～8.7%, 0.2%～1.7%, 0.2～1.7%, 8.0%～33.5%, 0.2～1.7% and 0.02%～0.1%.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述深色颜料为：氧化铁黑、苯胺黑、炭黑、硫化锑、氧化铁红、有机颜料红中的一种或两种。The green concrete for inducing the adhesion of marine sessile organisms according to claim 11, wherein the dark pigment is one of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red, and organic pigment red. Kind or two kinds.
根据权利要求12所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的深色颜料，根据对混凝土的性能影响程度，进行这些颜料的改性，采用透明树脂、有机硅、二甲硅氧烷、超疏水材料中的一种进行改性处理。The green concrete for inducing the adhesion of marine sessile organisms according to claim 12, characterized in that: the dark pigments are modified according to the degree of influence on the performance of the concrete, using transparent resin, silicone, two One of methicone and superhydrophobic materials is modified.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的生物钙粉为牛骨粉与生物碳酸钙粉包括牡蛎壳粉、鱼骨粉、鸡蛋壳粉、珊瑚粉中的一种或几种复合，其细度为100目～1000目。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, characterized in that the biological calcium powder is bovine bone powder and biological calcium carbonate powder, including oyster shell powder, fish bone powder, egg shell powder, and coral powder. One or several kinds of compound, and its fineness is 100 mesh to 1000 mesh.
根据权利要求14所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的生物钙粉，对100目到500目间的牡蛎壳粉、鸡蛋壳粉、珊瑚粉、鱼骨粉采用以下酸进行处理，包括乙酸、醋酸、硅酸、亚硫酸中的一种或两种；以及对100目到500目牛骨粉采用以下酸进行处理，包括稀释的磷酸、硫酸、盐酸和硝酸中的一种或两种。The green concrete for inducing the attachment of marine sessile organisms according to claim 14, characterized in that the biological calcium powder uses the following for oyster shell powder, egg shell powder, coral powder, and fish bone powder between 100 mesh and 500 mesh Acid treatment, including one or two of acetic acid, acetic acid, silicic acid, and sulfurous acid; and the treatment of 100 mesh to 500 mesh cattle bone meal with the following acids, including one of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid Kind or two kinds.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的胶凝材料为硫铝酸盐水泥、碱激发胶凝材料中的一种；硫铝酸盐水泥，包括快硬硫铝酸盐水泥、高强硫铝酸盐水泥、膨胀硫铝酸盐水泥中的一种或两种；碱激发胶凝材料为碱激发矿渣、碱激发矿渣+粉煤灰。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, characterized in that: the cementing material is one of sulphoaluminate cement and alkali-activated cementing material; sulphoaluminate cement includes One or two of fast hardening sulphoaluminate cement, high-strength sulphoaluminate cement, and expanded sulphoaluminate cement; alkali-activated cementitious materials are alkali-activated slag, alkali-activated slag + fly ash.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的生物碳酸钙颗粒为牡蛎壳、珊瑚其中的一种或两种，其颗粒的尺寸为0.16～5.0mm，并符合II区中砂的级配，用来取代混凝土配合比中的砂。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, characterized in that the biological calcium carbonate particles are one or two of oyster shells and corals, and the size of the particles is 0.16～5.0mm, It is in line with the sand gradation in Zone II and is used to replace the sand in the concrete mix.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的改性的碳酸盐、碳酸氢盐是碳酸钠、碳酸钾，碳酸氢钙、碳酸氢钠、碳酸氢钾中的一种或几种，采用硅藻土作为载体，与这些无机盐复合后实现相应离子的缓释及减少或者消除对混凝土性能的不良影响。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, wherein the modified carbonate and bicarbonate are sodium carbonate, potassium carbonate, calcium bicarbonate, sodium bicarbonate, and bicarbonate. One or more of potassium uses diatomaceous earth as a carrier to achieve the slow release of corresponding ions and reduce or eliminate adverse effects on concrete performance after being compounded with these inorganic salts.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述的砂为河砂、机制砂或者淡化海砂中的一种或几种。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, wherein the sand is one or more of river sand, machine-made sand or desalinated sea sand.
一种诱导海洋固着生物附着的绿色混凝土的制备方法，其特征在于，包括如下步骤：A preparation method of green concrete for inducing the attachment of marine sessile organisms, which is characterized in that it comprises the following steps:

S1：精确称量胶凝材料、碎石、砂、水、深色颜料、生物钙粉、生物碳酸钙颗粒、改性的碳酸盐或碳酸氢盐和超塑化剂；S1: Accurately weigh cementitious materials, gravel, sand, water, dark pigments, biological calcium powder, biological calcium carbonate particles, modified carbonate or bicarbonate and superplasticizer;

S2：先将碎石、砂、生物碳酸钙颗粒放入混凝土搅拌机中搅拌0.5～1分钟；然后加入胶凝材料、生物钙粉、深色颜料及改性的碳酸盐或碳酸氢盐，再继续搅拌0.5～1分钟；然后加入水和超塑化剂搅拌2～6分钟；搅拌均匀后，进行浇筑、振捣，随后进行标准养护28d或根据实际情况进行养护，即可制得一种诱导效果良好的海洋固着生物附着的绿色混凝土。S2: Put the gravel, sand and biological calcium carbonate particles into the concrete mixer and mix for 0.5 to 1 minute; then add the cementitious material, biological calcium powder, dark pigment and modified carbonate or bicarbonate, and then Continue to stir for 0.5 to 1 minute; then add water and superplasticizer and stir for 2 to 6 minutes; after stirring evenly, pour, vibrate, and then carry out standard curing for 28 days or curing according to the actual situation to obtain an induction Green concrete with good effect on marine anchorage.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述绿色混凝土由深色颜料、胶凝材料、碎石、砂、水和超塑化剂制成，深色颜料、胶凝材料、碎石、砂、水和超塑化剂重量配比依次为：0.2％～1.7％、13.3％～22.8％、39.4％～49.8％、8.0％～24.6％、6.2％～8.7％和0.02％～0.1％。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, characterized in that: the green concrete is made of dark pigment, cementitious material, gravel, sand, water and superplasticizer. , The weight ratio of cementing material, crushed stone, sand, water and superplasticizer are: 0.2%～1.7%, 13.3%～22.8%, 39.4%～49.8%, 8.0%～24.6%, 6.2%～8.7 % And 0.02%～0.1%.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述绿色混凝土由生物钙粉、胶凝材料、碎石、砂、水和超塑化剂制成，生物钙粉、胶凝材料、碎石、砂、水和超塑化剂重量配比依次为：0.2％～1.7％、13.3％～22.8％、39.4％～49.8％、8.0％～24.6％、6.2％～8.7％和0.02％～0.1％。The green concrete for inducing the attachment of marine fixed organisms according to claim 11, characterized in that: the green concrete is made of biological calcium powder, cementitious material, gravel, sand, water and superplasticizer, and biological calcium powder , The weight ratio of cementing material, crushed stone, sand, water and superplasticizer are: 0.2%～1.7%, 13.3%～22.8%, 39.4%～49.8%, 8.0%～24.6%, 6.2%～8.7 % And 0.02%～0.1%.
根据权利要求11所述的诱导海洋固着生物附着的绿色混凝土，其特征是：所述绿色混凝土由深色颜料、胶凝材料、碎石、砂、水、碳酸盐或碳酸氢盐和超塑化剂制成，深色颜料、胶凝材料、碎石、砂、水、碳酸盐或碳酸氢盐和超塑化剂重量配比依次为：0.2％～1.7％、13.3％～22.8％、39.4％～49.8％、8.0％～24.6％、6.2％～8.7％、0.2～1.7％和0.02％～0.1％。The green concrete for inducing the attachment of marine sessile organisms according to claim 11, characterized in that: the green concrete is made of dark pigment, cementitious material, gravel, sand, water, carbonate or bicarbonate and superplastic The weight ratio of dark pigment, gelling material, gravel, sand, water, carbonate or bicarbonate and superplasticizer is 0.2% to 1.7%, 13.3% to 22.8%, 39.4%～49.8%, 8.0%～24.6%, 6.2%～8.7%, 0.2～1.7% and 0.02%～0.1%.