CN103601415B - A kind of Concrete alkaline-adjustment microcapsule and preparation method thereof - Google Patents
A kind of Concrete alkaline-adjustment microcapsule and preparation method thereof Download PDFInfo
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- CN103601415B CN103601415B CN201310535283.5A CN201310535283A CN103601415B CN 103601415 B CN103601415 B CN 103601415B CN 201310535283 A CN201310535283 A CN 201310535283A CN 103601415 B CN103601415 B CN 103601415B
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Abstract
The invention discloses a kind of Concrete alkaline-adjustment microcapsule and preparation method thereof.Concrete alkaline-adjustment microcapsule comprises capsule-core and dressing, and described capsule-core comprises water-soluble alkaline oxide compound and forming agent, and described dressing comprises the organic materials to low alkali environment sensitive; Described water-soluble alkaline oxide compound is one or more in calcium oxide, potassium oxide and sodium oxide.Concrete alkaline-adjustment microcapsule of the present invention has satisfactory stability, by the change of the quality proportioning of core materials and coating material, the rate of release of inhibiter can accomplish optimized controllable, promote PH with water-soluble alkaline oxide compound and reach the object delaying concrete carbonization and reinforcing bar inhibition, the equal environmental protection of material therefor.So Concrete alkaline-adjustment microcapsule of the present invention has optimized controllable, validity period is long, had good sustained release effect and the effect of environmental protection.
Description
[technical field]
The present invention relates to concrete inhibiter capsule, particularly relate to a kind of Concrete alkaline-adjustment microcapsule and preparation method thereof.
[background technology]
Steel Concrete is as the representative of traditional building material, it has the features such as ultimate compression strength is high, weather resistance is strong, cost is low, be widely used in the works such as industry and covil construction, bridge, road engineering, underground works, Hydraulic and Hydro-Power Engineering, harbour and oceanographic engineering, at present again towards the infiltration of large-span structure, tall and slender structure, mammoth structure and unique construction, be apply to obtain material of construction the most widely.In existing RC structures; along with the impact of long-term use and around environment; especially under being in littoral environment; inevitably there is corrosion in the reinforcing bar implanted in concrete; Bearing Capacity of Reinforced Concrete Structures is caused significantly to reduce; the lighter can reduce structure work-ing life, and severe one entail dangers to structural safety, brings massive losses to national economy.Therefore, the reinforcing bar problem of rustiness in in-service Steel Concrete is the technical barrier of long-standing problem civil engineering work personnel.
Research shows that the major cause of reinforcing bar spontaneous corrosion in concrete comprises two aspects: 1) concrete carbonization causes the environmental PH at reinforcing bar place to reduce destroying rebar surface passive film and corrosion; 2) chlorine ion concentration is excessive, and research shows that chlorine ion concentration/hydroxide ion concentration >0.6 easily corrosion occurs.
Some scholars propose to add inhibiter in Steel Concrete preparation process, and wherein nitrites more typically represents, but use this method, and inhibiter a large amount of losses in the early stage make its effect in reinforcing bar inhibition be very little.
[summary of the invention]
The technical problem to be solved in the present invention is to provide a kind of intellectuality, effective Concrete alkaline-adjustment microcapsule and preparation method thereof is become rusty in resistance.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, a kind of Concrete alkaline-adjustment microcapsule comprises capsule-core and dressing, and described capsule-core comprises water-soluble alkaline oxide compound and forming agent, and described dressing comprises the organic materials to low alkali environment sensitive; Described water-soluble alkaline oxide compound is one or more in calcium oxide, potassium oxide and sodium oxide.
Above-described Concrete alkaline-adjustment microcapsule, described forming agent comprises thickening material, dispersion agent and tackiness agent; The described organic materials to low alkali environment sensitive is ethyl cellulose, polystyrene resin or polyacrylic resin.
Above-described Concrete alkaline-adjustment microcapsule, described capsule-core is made up of following proportioning by weight:
Above-described Concrete alkaline-adjustment microcapsule, the diameter of capsule-core is 0.3 millimeter to 0.5 millimeter, and the diameter of capsule is 0.35 millimeter to 1.5 millimeters.
Above-described Concrete alkaline-adjustment microcapsule, the weight ratio of capsule-core and dressing is 1:0.25-0.4.
A preparation method for above-mentioned Concrete alkaline-adjustment microcapsule, comprises the following steps:
601) preparation of capsule-core: after water-soluble alkaline oxide compound, forming agent and solvent, drop into extrusion spheronization machine and be extruded into strip, strip material is poured in the cylinder of extrusion spheronization machine round as a ball, then carries out drying treatment, obtained capsule-core;
602) coating liquid preparation: obtain coating liquid by dissolving the organic materials of low alkali environment sensitive in formula by the formula solvent of coating liquid;
603) spray coating: cylinder capsule-core being put into spray coating equipment, under dressing pattern, is sprayed onto the capsule-core of rolling on by coating liquid by the fog nozzle of equipment with pump;
604) dry: at temperature 30-40 DEG C, under force ventilated condition, dry 10-20 minute in the cylinder of drying plant, then Temperature fall, dry.
The preparation method of above-described Concrete alkaline-adjustment microcapsule, in step 601, capsule-core is made up of following proportioning by weight:
The preparation method of above-described Concrete alkaline-adjustment microcapsule, in step 602, coating liquid is formulated by following proportioning by weight:
Ethyl cellulose 100;
Ethanol 150-300;
Toluene 800-1000.
The preparation method of above-described Concrete alkaline-adjustment microcapsule, in step 602, coating liquid is formulated by following proportioning by weight:
Polystyrene 100;
Trichloromethane 900-1600.
The preparation method of above-described Concrete alkaline-adjustment microcapsule, the diameter of capsule-core is 0.3 millimeter to 0.5 millimeter, and the diameter of capsule is 0.35 millimeter to 1.5 millimeters; In capsule-core and coating liquid, the weight ratio of dry-matter is 1:0.25-0.4.
Concrete alkaline-adjustment microcapsule of the present invention has satisfactory stability, by the change of the quality proportioning of core materials and coating material, the rate of release of microcapsule can accomplish optimized controllable, promote PH with water-soluble alkaline oxide compound and reach the object delaying concrete carbonization and reinforcing bar inhibition, the equal environmental protection of material therefor.So Concrete alkaline-adjustment microcapsule of the present invention has optimized controllable, validity period is long, had good sustained release effect and the effect of environmental protection.
[accompanying drawing explanation]
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is embodiment of the present invention Concrete alkaline-adjustment microcapsule aspect graph under a scanning electron microscope.
Fig. 2 is the aspect graph of embodiment of the present invention Concrete alkaline-adjustment microcapsule under PH=13 environment.
Fig. 3 is the aspect graph of embodiment of the present invention Concrete alkaline-adjustment microcapsule under PH=11 environment.
Fig. 4 is the aspect graph of embodiment of the present invention Concrete alkaline-adjustment microcapsule under PH=9 environment.
Fig. 5 is the aspect graph of embodiment of the present invention Concrete alkaline-adjustment microcapsule under PH=7 environment.
[embodiment]
Below by embodiment, the present invention is further elaborated:
One, the embodiment of the preparation method of Concrete alkaline-adjustment microcapsule:
1. the preparation of capsule-core:
The each embodiment raw material mass mixture ratio of table 1. capsule-core
Wherein:
Calcium oxide (Chengdu Ke Long chemical reagent factory, analytical pure);
Ethanol (Chengdu Ke Long chemical reagent factory, analytical pure), as solvent;
Microcrystalline Cellulose (Anhui Shanhe Medicinal Subsidiary Material Co., Ltd., mountains and rivers board) is as thickening material;
Tween 80 (Guangdong, Guangdong emigrant's reagent plastics company limited, Guangdong emigrant's board) is as dispersion agent;
Vltra tears (Ningjin, Shandong De Xin Mierocrystalline cellulose company limited) is as tackiness agent.
Capsule-core is preparation method comprise the following steps:
1) capsule-core preparation: by the capsule-core proportioning of table 1, first 50% ethanol is fully mixed with Microcrystalline Cellulose and Vltra tears, then add water-soluble alkaline oxidation physical property material, finally add tween 80, stir, 50% ethanol is evenly existed in the mixture;
2) extrude take out thin: the charging opening of above-mentioned mixture at extrusion equipment is dropped into, extrudes the core materials of rice noodles strip;
3) discharging is round as a ball: by described rice noodles strip core materials, pour the cylinder in rolling circle equipment into, roll out capsule-core particulate;
4) dry: capsule-core to be rolled out in the cylinder of particulate drying plant, under drying temperature 30-40 DEG C of force ventilated condition, carry out drying treatment, obtain through screen cloth the capsule-core particulate that diameter is 0.3 millimeter to 0.5 millimeter.
2. the preparation of coating liquid:
The each embodiment raw material mass mixture ratio of table 2. dressing:
Wherein:
Toluene (Chengdu Ke Long chemical reagent factory, analytical pure), as solvent;
Ethyl cellulose (Guangzhou Dao Jun Chemical Industry Science Co., Ltd), is used as the organic materials to low alkali environment sensitive;
Ethanol (Chengdu Ke Long chemical reagent factory, analytical pure), as solvent;
Coating liquid preparation comprises the following steps: by the proportioning of table 2, and first by toluene and ethanol mixing, then ethyl cellulose added in toluene and alcohol mixeding liquid, uniform stirring, heating in water bath remains on 60 degrees Celsius, makes coating liquid.
Continued 2:
Wherein:
Polystyrene (Pu Zhen bio tech ltd, Shanghai), is used as the organic materials to low alkali environment sensitive;
Trichloromethane (Chengdu Ke Long chemical reagent factory, analytical pure), as solvent;
During coating liquid preparation, be that 1:0.25 to 1:4 takes coating material by the weight ratio of capsule-core and coating material dry-matter, coating material weight proportion performs by table 2.By adjustment capsule-core and the weight ratio of coating material dry-matter and the thickness of adjustable dressing (cyst wall), realize the adjustment to microcapsule rate of release.
3. spray coating: the cylinder dried capsule-core particle being put into again extrusion spheronization machine, starts dressing pattern, connects fog nozzle and coating liquid with pump, adjustment hydrojet speed (air blast flux 2200L/h; Spray pressure 0.2Mpa, till coating liquid has sprayed completely.
After microcapsule after spraying are carried out drying (drying temperature 30-40 DEG C, time 10-20 minute), take out to spread out and appoint so cooling, dry and obtain capsule finished product.
The above embodiment calcium oxide of the present invention is described as the representative of water-soluble alkaline oxide compound, and the calcium oxide in capsule-core can use sodium oxide, potassium oxide or its mixture replacing.
The particle diameter of the ethyl cellulose type calcium oxide microcapsule prepared by preparation method of the present invention can be 0.35-1.5 millimeter, the weight ratio of the particle diameter 0.35 millimeter corresponding capsule-core/coating material dry-matter of microcapsule is 1:0.1), the weight ratio=1:0.4 of the corresponding capsule-core coating material dry-matter of particle diameter 1.5 millimeters of microcapsule).
In the preferred embodiment, capsule-core quality mixture ratio is calcium oxide: Microcrystalline Cellulose: 50% ethanol: Vltra tears: tween 80=100:96:120:2:10.Coating liquid quality mixture ratio ethyl cellulose: toluene alcohol mixeding liquid=1:10(wherein, toluene: ethanol=4:1), polystyrene resin: trichloromethane=1:10.
In practice, capsule can adopt the dressing of any one capsule-core and any one embodiment in embodiment 1-5 to arrange in pairs or groups, and makes required Concrete alkaline-adjustment microcapsule.
Below with core materials and be coating material respectively for embodiment 1, the weight ratio of capsule-core and coating material dry-matter is 1:0.25, and capsule grain diameter is that the Concrete alkaline-adjustment microcapsule of 0.5 millimeter is described.
Two, the microscopic appearance of ethyl cellulose type calcium oxide microcapsule:
As shown in Figure 1, the form of scanning electronic microscope to embodiment of the present invention microcapsule is utilized to take, observe and find microcapsule size uniform particles, shape presents ellipsoid shape, and it is concavo-convex with some, analyze its major cause, mainly and high-pressure fog process medium speed round as a ball at capsule-core particle and not exclusively evenly caused by.Consider the irregularities of concrete material internal pore structure, therefore the regularity of its form there is no material impact to its use.
Three, the stability of ethyl cellulose type calcium oxide microcapsule:
Get the beaker of two 500ml, measure 500ml ultrapure water be poured in beaker with 500ml graduated cylinder, weigh with scale lime powder and each 3g of calcium oxide microcapsule, puts into beaker and observe its stability.After 24 hours under the protection of dressing, microcapsule still present graininess in aqueous, and calcium oxide is thoroughly dissolved.
Four, the releasing rule of ethyl cellulose type calcium oxide microcapsule:
Be 13,11 at PH, under four kinds of environment of 9,7, add the above-mentioned microcapsule corrosion inhibitor of 20g respectively, at different time observation microcapsule capsule-core releasing ratio.Experimental result shows:
1) in the same time period, along with the reduction microcapsule capsule-core burst size of ph value increases;
2) under same pH value condition, along with the prolongation microcapsule capsule-core burst size of time increases.
Electron-microscope scanning figure shown in Fig. 2 to Fig. 5 has confirmed the above results.Prove that chemistry of the present invention goes out to trigger microcapsule corrosion inhibitor and has change to pH value and the function triggered.
The present invention utilizes spray-drying process to prepare microcapsule, its cardinal principle utilizes high-pressure sprayer to spray the liquid high polymeric solution that can bond capsule-core particle surface to the capsule-core particle surface operated in cylinder high speed, by high temperature, high polymer solvent evaporated and form a kind of Micro-Encapsulation Technique of high-polymer membrane on its surface after sprinkling.The present invention utilizes coating material to be sprayed at core materials to prepare a kind of Concrete alkaline-adjustment microcapsule just.
Experimental result can be found out, microcapsule have satisfactory stability, and the change of quality proportioning by core materials and coating material, the rate of release of microcapsule can accomplish optimized controllable, thus reaches and effectively solve capsule-core and easily run off and the object of controllable release.
Research shows, the major cause of the reinforcing bar spontaneous corrosion in concrete comprises two aspects: 1) concrete carbonization causes the environmental PH at reinforcing bar place to reduce destroying rebar surface passive film and corrosion; 2) chlorine ion concentration is excessive, and research shows that chlorine ion concentration/hydroxide ion concentration >0.6 easily corrosion occurs.
The Concrete alkaline-adjustment microcapsule of the above embodiment of the present invention is based on ion-trigger and can promotes the microcapsule of stabilizing concrete environment pH value.Different from traditional microcapsules, microcapsule involved in the present invention, its cyst wall has chemistry and triggers (as carbanion, chlorion, sulfate ion, pH value etc.) function, its capsule-core has the function of lifting and stabilizing concrete pH value, solves the problems such as Steel Concrete performance degradation, steel bar corrosion from root.
When Steel Concrete generation carbonization, the pH value in concrete can reduce, and rebar surface passive film is destroyed and easily corrosion occurs.Concrete alkaline-adjustment microcapsule of the present invention, containing water-soluble alkaline oxide compound in capsule-core, as calcium oxide, potassium oxide and sodium oxide etc., when in concrete environment, pH value declines for a certain reason time, cyst wall is triggered and surface produces structural defect, capsule-core water-soluble alkaline oxide compound is taken out of by water dissolution, dissolution equilibrium can be formed inside and outside capsule-core, directly can promote the pH value of concrete environment, and stablize pH value over a period to come, delayed the object of concrete carbonization and reinforcement corrosion from root, this is consistent with the function of inhibiter.If directly add water-soluble alkaline oxide compound in concrete, can not long-term stability be present in concrete because it is soluble in water.
The beneficial effect of the above embodiment of the present invention is as follows:
(1) utilize high-pressure spray-drying principle to form one deck barrier film on calcium oxide particle surface, barrier film makes core materials protected, and realizes the construction technology that capsule in whipping process directly mixes, and avoids the impact of constructing on core materials;
(2) construction technology of directly mixing makes capsule be randomly distributed in each position of concrete, and the ion of the extraneous all directions of corresponding antagonism and carbonic acid gas invasion, some capsule can directly arrive reinforced concrete surface and play corrosion mitigating effect.
(3) adopt water-soluble alkaline oxide compound directly to promote the theory of pH value, both stabilized concrete pH value, and delayed again concrete carbonization, succinctly easy to operate, easy to implement, remarkably productive, delay concrete durability from root.
The microcapsule be successfully prepared can the thickness of experimental effect adjustment dressing realize discharging the intelligence of capsule-core, microcapsule are made to adjust the speed of its release by the change of the external stimulus environment estimated, capsule-core burst size also can make change according to its solubleness, realizes the change for external environment and the object of mobile reactant.
Claims (7)
1. a Concrete alkaline-adjustment microcapsule, comprises capsule-core and dressing, it is characterized in that, described capsule-core comprises water-soluble alkaline oxide compound and forming agent, and described dressing comprises the organic materials to low alkali environment sensitive; Described water-soluble alkaline oxide compound is one or more in calcium oxide, potassium oxide and sodium oxide;
Described capsule-core is made up of following proportioning by weight:
Described forming agent comprises thickening material, dispersion agent and tackiness agent; The described organic materials to low alkali environment sensitive is ethyl cellulose, polystyrene resin or polyacrylic resin.
2. Concrete alkaline-adjustment microcapsule according to claim 1, is characterized in that, the diameter of capsule-core is 0.3 millimeter to 0.5 millimeter, and the diameter of capsule is 0.35 millimeter to 1.5 millimeters.
3. Concrete alkaline-adjustment microcapsule according to claim 1, is characterized in that, the weight ratio of capsule-core and dressing is 1:0.25-0.4.
4. a preparation method for Concrete alkaline-adjustment microcapsule described in claim 1, is characterized in that, comprises the following steps:
401) preparation of capsule-core: after water-soluble alkaline oxide compound, forming agent and solvent, drop into extrusion spheronization machine and be extruded into strip, strip material is poured in the cylinder of extrusion spheronization machine round as a ball, then carries out drying treatment, obtained capsule-core;
402) coating liquid preparation: obtain coating liquid by dissolving the organic materials of low alkali environment sensitive in formula by the formula solvent of coating liquid;
403) spray coating: cylinder capsule-core being put into spray coating equipment, under dressing pattern, is sprayed onto the capsule-core of rolling on by coating liquid by the fog nozzle of equipment with pump;
404) dry: at temperature 30-40 DEG C, under force ventilated condition, dry 10-20 minute in the cylinder of drying plant, then Temperature fall, dry;
In step 401, capsule-core is made up of following proportioning by weight:
5. the preparation method of Concrete alkaline-adjustment microcapsule according to claim 4, is characterized in that, in step 402, coating liquid is formulated by following proportioning by weight:
Ethyl cellulose 100;
Ethanol 150-300;
Toluene 800-1000.
6. the preparation method of Concrete alkaline-adjustment microcapsule according to claim 4, is characterized in that, in step 402, coating liquid is formulated by following proportioning by weight:
Polystyrene 100;
Trichloromethane 900-1600.
7. the preparation method of Concrete alkaline-adjustment microcapsule according to claim 4, is characterized in that, the diameter of capsule-core is 0.3 millimeter to 0.5 millimeter, and the diameter of capsule is 0.35 millimeter to 1.5 millimeters; In capsule-core and coating liquid, the weight ratio of dry-matter is 1:0.25-0.4.■
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| CN107673678B (en) * | 2017-11-03 | 2020-06-05 | 西安东大洋混凝土有限公司 | Recycled concrete and preparation method thereof |
| CN108070864B (en) * | 2017-12-25 | 2020-11-24 | 重庆工业职业技术学院 | pH value response intelligent control release corrosion inhibitor and preparation method thereof |
| CN108609880A (en) * | 2018-05-22 | 2018-10-02 | 深圳大学 | A kind of microcapsules and preparation method thereof and a kind of microcapsules armored concrete and preparation method thereof |
| CN108911632B (en) * | 2018-08-03 | 2021-02-19 | 上海住信住宅工业有限公司 | Concrete repairing material and preparation method thereof |
| CN109795020B (en) * | 2019-03-21 | 2021-04-23 | 徐州工程学院 | Preparation method of high-carbonization-resistance reinforced concrete |
| CN109824312B (en) * | 2019-03-21 | 2021-07-27 | 徐州工程学院 | Preparation method for improving chlorine ion erosion resistance of marine reinforced concrete |
| CN117229688B (en) * | 2023-09-05 | 2024-03-22 | 嘉丰盛精密电子科技(孝感)有限公司 | Coating of self-repairing material for vehicle and preparation method |
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| CN101289298A (en) * | 2008-05-20 | 2008-10-22 | 深圳大学 | Self-repair concrete using urea-formaldehyde resin type high molecule microcapsule and method of manufacture |
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