CN109733012B - Anti-fouling material based on bionic strengthening and toughening structure and preparation method thereof - Google Patents
Anti-fouling material based on bionic strengthening and toughening structure and preparation method thereof Download PDFInfo
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- CN109733012B CN109733012B CN201910000354.9A CN201910000354A CN109733012B CN 109733012 B CN109733012 B CN 109733012B CN 201910000354 A CN201910000354 A CN 201910000354A CN 109733012 B CN109733012 B CN 109733012B
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Abstract
The invention belongs to the technical field of marine antifouling materials, and particularly relates to an antifouling material based on a bionic toughening structure and a preparation method thereof, wherein the antifouling material based on the bionic toughening structure is a fiber-organic silicon composite material, fiber layers are vertically overlapped according to the fiber direction to form a multilayer spiral shell-like fiber structure, and the antifouling material has the antifouling property of the organic silicon antifouling material and higher mechanical strength; the antifouling material has obvious adhesion and growth inhibition effects on typical fouling organisms, has toughness, simple preparation method, easily-controlled reaction conditions and easily-obtained raw materials, has potential application prospects, can be fixed on underwater parts of ocean engineering facilities in a sticking, riveting, coating or splicing mode, and plays a role in preventing and removing fouling organism adhesion.
Description
The technical field is as follows:
the invention belongs to the technical field of marine antifouling materials, and particularly relates to an antifouling material based on a bionic strengthening and toughening structure and a preparation method thereof.
Background art:
marine biofouling can cause serious damage to underwater facilities such as ships, marine engineering facilities and the like: increase the ship navigation resistance, destroy the protective coating of the facilities, block the sea pipeline and the like. The marine antifouling material is the main method for preventing and eliminating the fouling of underwater organisms on the outer surface of ships and marine engineering. The marine antifouling material mainly comprises a film-forming resin material, pigments, fillers and other solid components, and can be classified into acrylic acids, chlorinated rubbers, organic silicon and fluorocarbon resins according to the difference of the resin material. Among them, the silicone antifouling materials have the characteristics of environmental protection, drag reduction, non-stick surface, no biocide content and the like, and have been rapidly developed in recent years. Internatual Paint, Chugaku, Sigma, Hempel, and Guanxi Paint have proposed Intersleep series, Seajet series, Sigmalide series, Hempasil X series, and Captain Biox series silicone antifouling Paint products, respectively. U.S. Pat. No. 2,264,2778 proposes an antifouling paint with low surface energy based on silicone rubber for the first time, but the antifouling effect is not as good as that of the traditional antifouling paint. Subsequently, japanese patents JP9118877 and JP9276977 disclose antifouling materials using room temperature vulcanized silicone rubber as a base, japanese patent JP13286186A discloses low surface energy antifouling paints prepared using a polymer synthesized from an unsaturated polysiloxane, an unsaturated siloxane and a polymerizable unsaturated vinyl monomer as a base, japanese patents JP27847687, JP15723287, JP15723187, JP16074887, JP16074787 and JP16074987 disclose a series of modified silicone-based antifouling paints, which indicate new directions for improving application properties such as adhesion and the like for silicone resin low surface energy antifouling paints, based on which silicone antifouling paints are rapidly developed thereafter: european patent EP89301373 discloses an antifouling paint based on polyurethane modified silicone, polysiloxane elastomer is prepared by interpenetration of polysiloxane networks crosslinked by polyurethane or polyurea, Japanese patent JP5960990 discloses silicone modified epoxy resin, and amino alkoxy silane is used as curing agent to obtain silicone antifouling paint with good hardness and adhesion, U.S. Pat. No. 4,692,821 discloses self-polishing antifouling paint containing siloxane resin, which combines the hydrolysis characteristic of self-polishing paint and the low surface performance of siloxane resin paint, and has good storage stability and adhesion, Japanese patent JP2007070385A discloses a method for introducing polyvinyl alcohol into alkoxy silane to make paint have good adhesion, Chinese patent CN1210357C discloses low surface energy antifouling paint using polysiloxane and fluoropolymer as main film-forming substances, Chinese patent CN1203152C discloses polydimethylsiloxane as main film-forming substance, the super-hydrophobic organic silicon antifouling material is prepared by matching silica gel and silica particles.
At present, the application performances such as adhesive force and the like of the organic silicon antifouling material are improved through years of research, but the problems of low mechanical strength, easy scratching and damage on the surface, easy cracking after long-term use and the like still exist. Therefore, increasing the toughness of the silicone antifouling material to avoid failure caused by breakage in the use process is a critical technology which needs to be solved urgently. There are many natural tough materials in nature with good mechanical properties, such as shells of marine Baospira: the shell is a natural tough material composed of a biological ceramic composite material, the shell is similar to a brick-slurry composite structure in a microscopic structure, the brick is composed of calcium carbonate aragonite slices, slurry is composed of protein and organic matters, the brick-slurry structure is assembled layer by layer and is distributed in a three-dimensional manner, and the shell has excellent mechanical properties due to the staggered micro-nano structure and components, so that the shell has reference significance for improving the strength and toughness of the material. Scanning electron microscope observation is carried out on the bending fracture surface of the snail shell of the geosnails (Cypraageogaphca) to obtain a graph 1, an obvious fibrous structure can be observed, the fibers are arranged in a stacking and staggered mode and used as a reference for bionic strengthening and toughening structure design, a snail shell-like layered composite microstructure is added into the antifouling material, and carbon fibers or silicon carbide fibers with tensile strength reaching 2-6GPa grade are used as reinforcing components, so that the mechanical strength of the antifouling material is improved.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops and designs an antifouling material based on a bionic strengthening and toughening structure and a preparation method thereof.
In order to achieve the aim, the main body structure of the antifouling material based on the bionic toughening structure comprises a transverse fiber layer and a longitudinal fiber layer, wherein the transverse fiber layer and the longitudinal fiber layer are vertically overlapped according to the fiber direction to form a multilayer structure; the number of the superposed layers of the transverse fiber layers and the longitudinal fiber layers is 2-20; the transverse fiber layer and the longitudinal fiber layer are both carbon fiber-organic silicon composite materials or silicon carbide fiber-organic silicon materials, the carbon fiber-organic silicon composite materials are composed of carbon fibers and organic silicon rubber, and the silicon carbide fiber-organic silicon materials are composed of silicon carbide fibers and organic silicon rubber.
The technological process of the preparation method of the antifouling material based on the bionic strengthening and toughening structure comprises four steps of activation, modification, reaction and solidification:
(1) and (3) activation: carrying out surface activation treatment on the fiber by using air plasma to generate hydroxyl groups on the surface of the fiber;
the fiber is bundle monofilament or cross-woven carbon fiber or silicon carbide fiber;
(2) modification: fixing the two layers of fibers which are respectively fixed into 1 fiber layer, wherein the two layers of fibers are vertically crossed, the vertical distance between the two layers of fibers is 0.4-2mm, and modifying 1-10 fiber layers by using a silane coupling agent;
silane coupling agents include, but are not limited to, KH550, KH560, KH570, KH580, KH602, and KH 792;
(3) reaction: reacting the modified fiber layer with hydroxyl silicone oil with the viscosity of 3000-10000cps for 1-3h at the temperature of 100-140 ℃;
(4) and (3) curing: uniformly mixing hydroxyl silicone oil with the hydroxyl content of 5-12%, tetraethoxysilane and butyltin dilaurate to form a mixed solution, wherein the mass percentages of the hydroxyl silicone oil, tetraethoxysilane and butyltin dilaurate in the mixed solution are respectively 60-75%, 5-20% and 10-20%, and placing the fiber layer reacted with the hydroxyl silicone oil in the mixed solution for curing for 36-72h under the normal temperature condition to prepare the antifouling material based on the bionic strengthening and toughening structure.
The antifouling material based on the bionic strengthening and toughening structure is a film-shaped flexible material, the surface to be protected is covered in a sticking, rivet fixing, cladding or splicing mode according to different application parts of marine facilities, the antifouling material based on the bionic strengthening and toughening structure is in direct contact with seawater, and the antifouling effect is achieved by utilizing the characteristics of organic silicon.
Compared with the prior art, the antifouling material based on the bionic strengthening and toughening structure is a fiber-organic silicon composite material, the fiber layers are vertically overlapped according to the fiber direction to form a multilayer spiral shell-like fiber structure, the antifouling property of the organic silicon antifouling material is achieved, the mechanical strength is high, the inhibition test result on fouling organisms shows that the adhesion inhibition rate on the small-boat-shaped diatom reaches 85 percent, the adhesion desorption rate reaches 92 percent, the inhibition rate on the adhesion of mussel byssus reaches 80 percent, meanwhile, the tensile strength reaches 12MPa and is improved by more than 10 times compared with the strength of the organic silicon material without fibers, the preparation method has the technical processes that the carbon fiber/silicon carbide fiber subjected to surface activation is orderly arranged and modified by a silane coupling agent, then the carbon fiber/silicon carbide fiber is reacted with hydroxyl silicone oil at high temperature, and finally, the mixed solution of the hydroxyl silicone oil, ethyl orthosilicate and butyltin dilaurate is solidified into the film-shaped flexible bionic strengthening and toughening-based on the bionic strengthening and toughening flexibility at normal Structured anti-fouling materials; the antifouling material has obvious adhesion and growth inhibition effects on typical fouling organisms, has toughness, simple preparation method, easily-controlled reaction conditions and easily-obtained raw materials, has potential application prospects, can be fixed on underwater parts of ocean engineering facilities in a sticking, riveting, coating or splicing mode, and plays a role in preventing and removing fouling organism adhesion.
Description of the drawings:
fig. 1 is a schematic view of a scanning electron microscope of a bending fracture surface of a geobanil shell according to the background art of the present invention.
FIG. 2 is a schematic diagram of the principle of the main structure of the antifouling material based on the bionic toughening structure.
FIG. 3 is a process flow diagram of a method for preparing an antifouling material based on a bionic strengthening and toughening structure according to the invention.
FIG. 4 is a schematic diagram of a process flow of a method for preparing an antifouling material based on a bionic toughening structure in example 1 of the present invention.
FIG. 5 is a schematic view of the fixing of fibers according to step 2 of example 1 of the present invention.
The specific implementation mode is as follows:
the invention is further described by way of example with reference to the accompanying drawings.
Example 1:
the main body structure of the antifouling material based on the bionic toughening structure comprises a transverse fiber layer 1 and a longitudinal fiber layer 2, wherein the transverse fiber layer 1 and the longitudinal fiber layer 2 are vertically overlapped according to the fiber direction to form a multilayer structure; the number of the superposed layers of the transverse fiber layer 1 and the longitudinal fiber layer 2 is 2-20; the transverse fiber layer 1 and the longitudinal fiber layer 2 are both carbon fiber-organic silicon composite materials or silicon carbide fiber-organic silicon materials, the carbon fiber-organic silicon composite materials are composed of carbon fibers and organic silicon rubber, and the silicon carbide fiber-organic silicon materials are composed of silicon carbide fibers and organic silicon rubber.
Example 2:
the technological process route of the preparation method of the antifouling material based on the bionic toughening structure is shown in fig. 4, and the technological process comprises four steps of activation, modification, reaction and curing:
(1) and (3) activation: activating the surface of the fiber by using air plasma to generate hydroxyl groups on the surface of the fiber;
the fiber is bundle-shaped monofilament carbon fiber;
(2) modification: according to the fixing mode shown in fig. 5, an upper part and a lower part of a fixture are used, fibers are placed on the lower part, four movable clamping pieces on the upper part are divided into two groups, the fibers in two directions are clamped respectively, the parallel and uniform fibers are fixed by the fixture, the fibers on the lower layer are fixed firstly, then the fibers on the upper layer are fixed, the fibers are divided into an upper layer and a lower layer, the fibers on the two layers are vertically crossed, the vertical gap between the fibers on the two layers is 2mm, the fibers on the two layers are clamped by a dovetail clamp and fixed into 1 fiber layer, and the fiber layers are modified by using a silane coupling agent KH;
(3) reaction: reacting the modified fiber layer with hydroxyl silicone oil with the viscosity of 5000cps for 2h at the temperature of 120 ℃;
(4) and (3) curing: uniformly mixing hydroxyl silicone oil with the hydroxyl content of 10%, ethyl orthosilicate and butyltin dilaurate according to the mass ratio of 70:15:15 to form a mixed solution, and placing a fiber layer reacted with the hydroxyl silicone oil in the mixed solution for curing for 50 hours at normal temperature to prepare the antifouling material based on the bionic toughening structure.
Example 3:
the tensile strength of the antifouling material based on the bionic toughening structure prepared in the example 1 is 12MPa by adopting GB/T528-2009 (determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber), and the tensile strength of the antifouling material without fibers is 1 MPa.
Example 4:
the embodiment relates to an antifouling performance test of an antifouling material based on a bionic toughening structure: the antifouling material based on the bionic toughening structure prepared in example 1 is added into the solution with the concentration of 105Standing the solution for 24h in each mL of scaphoid diatom solution under the conditions that the temperature is 25 ℃, the illumination intensity is 1900lux and the light and shade period is 12 h: 12h, counting the attached scaphoid diatoms, and calculating the inhibition rate of the attachment of the scaphoid diatoms to blank glass to be 85%; flushing the antifouling material attached with the small navicula diatoms and based on the bionic strengthening and toughening structure for 5min by using water flow with the flow speed of 2m/s, counting the remaining attached small navicula diatoms, and calculating the removal rate of the small navicula diatoms to be 92%; add into mussel test plate based on the antifouling material of the structure of obleicacizing bionically, 10 mussels are placed to every plate, 24h back test is based on the adnexed byssus quantity of the antifouling material of the structure of obleicacizing bionically, relative blank glass, the antifouling material based on the structure of obleicacizing bionically is 80% to the adnexed rate of inhibition of mussel byssus, the result shows, antifouling material based on the structure of obleicacizing bionically can effectively restrain the bobo shape diatom and the mussel adheres to, have apparent prevention and removal effect to typical fouling.
Claims (2)
1. The antifouling material based on the bionic strengthening and toughening structure is characterized in that a main body structure comprises a transverse fiber layer and a longitudinal fiber layer, wherein the transverse fiber layer and the longitudinal fiber layer are vertically overlapped according to the fiber direction to form a multilayer structure; the number of the superposed layers of the transverse fiber layers and the longitudinal fiber layers is 2-20; the transverse fiber layer and the longitudinal fiber layer are both carbon fiber-organic silicon composite materials or silicon carbide fiber-organic silicon materials, the carbon fiber-organic silicon composite materials are composed of carbon fibers and organic silicon rubber, and the silicon carbide fiber-organic silicon materials are composed of silicon carbide fibers and organic silicon rubber; the preparation method of the antifouling material based on the bionic strengthening and toughening structure comprises the following four steps of activation, modification, reaction and curing:
(1) and (3) activation: carrying out surface activation treatment on the fiber by using air plasma to generate hydroxyl groups on the surface of the fiber;
the fiber is bundle monofilament or cross-woven carbon fiber or silicon carbide fiber;
(2) modification: fixing the two layers of fibers which are respectively fixed into 1 fiber layer, wherein the two layers of fibers are vertically crossed, the vertical distance between the two layers of fibers is 0.4-2mm, and modifying 1-10 fiber layers by using a silane coupling agent;
silane coupling agents include, but are not limited to, KH550, KH560, KH570, KH580, KH602, and KH 792;
(3) reaction: reacting the modified fiber layer with hydroxyl silicone oil with the viscosity of 3000-10000cps for 1-3h at the temperature of 100-140 ℃;
(4) and (3) curing: uniformly mixing hydroxyl silicone oil with the hydroxyl content of 5-12%, tetraethoxysilane and butyltin dilaurate to form a mixed solution, wherein the mass percentages of the hydroxyl silicone oil, tetraethoxysilane and butyltin dilaurate in the mixed solution are respectively 60-75%, 5-20% and 10-20%, and placing the fiber layer reacted with the hydroxyl silicone oil in the mixed solution for curing for 36-72h under the normal temperature condition to prepare the antifouling material based on the bionic strengthening and toughening structure.
2. The antifouling material based on the bionic toughening structure as claimed in claim 1 is a film-shaped flexible material, and according to different application positions of marine facilities, the surface to be protected is covered by pasting, riveting, cladding or splicing, and is in direct contact with seawater, and the antifouling effect is achieved by utilizing the characteristics of silicone.
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