CN108558260A - A kind of self union concrete complex enzyme microencapsulation material and preparation method thereof - Google Patents
A kind of self union concrete complex enzyme microencapsulation material and preparation method thereof Download PDFInfo
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- CN108558260A CN108558260A CN201810507938.0A CN201810507938A CN108558260A CN 108558260 A CN108558260 A CN 108558260A CN 201810507938 A CN201810507938 A CN 201810507938A CN 108558260 A CN108558260 A CN 108558260A
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- concrete
- complex enzyme
- calcium
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- microencapsulation material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a kind of self union concrete complex enzyme microencapsulation materials and preparation method thereof, the self union concrete complex enzyme microencapsulation material contains the component of following weight percent, urase 0.5~1%, hydrogenlyase 0.5~1%, oxidized nicotinamide adenine dinucleotide 0.5~1%, alcoholysis degree is more than 99.5% polyvinyl alcohol 0.05~0.3%, urea 18~24%, calcium formate 39~52%, calcic retarder 5~10% and silicon ash 10~30%, wherein urase, hydrogenlyase, oxidized nicotinamide adenine dinucleotide, first spray-dried technique is processed into microcapsules and is mixed again with other components with polyvinyl alcohol.The concrete for having used this self union concrete complex enzyme microencapsulation material of the invention, can make the crack self-healing of concrete in the presence of water, to improve the durability of concrete.
Description
Technical field
The present invention relates to the Techniques for Remedy of Cracks of civil engineering technology concrete protection field more particularly to concrete necks
Domain.
Technical background
Armored concrete is most commonly used construction material in the world today, and there is tiny capillarys for concrete material
Hole, under harsh corrosive environment, harmful ion is led using water as medium osmosis to inside concrete by physics, chemical action
It causes reinforcing bar and concrete to generate corrosion, eventually leads to structural failure.Wherein chlorion is to make steel by destroying rebar passivation film
Muscle corrosion expands；CO3 2-With Ca (OH)2In conjunction with make concrete pH value reduction；SO4 2-Ion makes to mix by physics, chemical action
Solidifying local products life internal expansion is destroyed.These corrosion factors all be unable to do without the participation of moisture, in addition under northern area freezing-thawing
Concrete destruction is directly with moisture penetration correlation, and the presence in crack accelerates the seepage velocity of moisture and harmful ion.Therefore,
The durability of concrete can be promoted by repairing the crack of concrete.Distress in concrete Producing reason is numerous, difficult in practice of construction
To avoid one by one, include mainly：Plastic Shrinkage of Concrete crack, coagulation dry shrinkage fracture, stress concentration crack, placement layer by layer
Lead to malformation cracking etc. caused by the restraint crack of concrete, uneven settlement of foundation.
The deterioration destructive process of concrete structure is mostly since various harmful substances are externally to internal infiltration or migration
Effect, thus the impermeability of concrete structure is to reflect an overall target of its durability.The presence in crack will directly affect
To the impermeability and durability of concrete, and since carbon dioxide and other harmful substances can quickly be penetrated by crack
To inside concrete, thus the carbonization speed of concrete will be far longer than at free from flaw at crack.Code for design of concrete structures
Middle permission concrete structure work with cracking, but fracture width has certain limitation, when concrete structure crack width is more than
After certain numerical value, water, oxygen, carbon dioxide and chlorion in environment etc., which are penetrated by crack in concrete, makes reinforcing bar become rusty
Erosion, eventually affects structural bearing capacity ability.Crack is different the extent of injury of structure durability under the conditions of varying environment.
The concrete component being especially under the conditions of underground, humidity or pernicious gas, works as fracture width>0.2mm, depth are more than protection
Layer thickness will cause the steel bar corrosion of concrete component.
The corrosion that the crack of concrete structure and the corrosion interaction of reinforcing bar can aggravate Steel Bars in Concrete Structure is broken
It is bad.On the one hand, the crack of concrete structure can increase the permeability of concrete, accelerate the carbonization of concrete and invading for etching medium
Erosion, makes the corrosion of reinforcing bar aggravate；On the other hand, the corrosion expansion of reinforcing bar can cause the further cracking of concrete again, thus into
One step aggravates the electrochemical corrosion of reinforcing bar.Above procedure ringing makes the durability of concrete structure substantially reduce.
The form in crack has reinforcement corrosion important influence, in contrast, is parallel to the longitudinal crack of main reinforcement, for knot
The influence of structure durability, serious more than the transverse crack perpendicular to main reinforcement, component damage is often by concrete along longitudinal direction along muscle
Cracking causes.After crack along bars occur, Speed of steel Corrosion is accelerated, and eventually leads to the peeling of protective layer sheet, bar diameter is substantially
Degree, which attenuates, to be even broken.It, can be tight once concrete is caused to occur cracking along muscle due to reinforcement corrosion in reinforced concrete structure
The service life of structure is reduced again.
Invention content
The first object of the present invention is to provide a kind of complex enzyme microencapsulation material that autogenous healing can be promoted to close.
The second object of the present invention is to provide the preparation method of above-mentioned complex enzyme microencapsulation material.
In order to realize above-mentioned first purpose, present invention employs following technical schemes：A kind of self union concrete complex enzyme
Microencapsulation material, the component containing following weight percent, urase 0.5~1%, hydrogenlyase 0.5~1%, oxidized form
The polyvinyl alcohol 0.05~0.3% of nicotinamide adenine dinucleotide 0.5~1%, alcoholysis degree more than 99.5%, urea 18~
24%, calcium formate 39~52%, calcic retarder 5~10% and silicon ash 10~30%, wherein urase, hydrogenlyase, oxidation
Type nicotinamide adenine dinucleotide, first to be processed into microcapsules mixed with other components again for spray-dried technique with polyvinyl alcohol
It closes.
The urea and calcium formate be ground into it is powdered, and in molar ratio be about 1：1 is uniformly mixed.
The calcic retarder is concrete retarder, and the purpose being added is to offset the rapid hardening effect of calcium formate, is powder
Last shape, in sugar calcium of the calcic retarder selected from dry powder doses, calcium gluconate, calcium citrate, calcium tartrate, wooden calcium sulfonate
One kind.
The silicon ash is concrete reinforcement material, and the purpose being added makes up leads to concrete because adding organic matter
Loss of strength.
In order to realize above-mentioned second purpose, present invention employs following technical schemes：
By the preparation method of upper any self union concrete complex enzyme microencapsulation material comprising following steps：
(1) dispensing；
(2) urase, hydrogenlyase, oxidized nicotinamide adenine dinucleotide and polyvinyl alcohol is first dry through spraying
Drying process is processed into microcapsules；
(3) obtained microcapsules are mixed with other components.
The generation of distress in concrete leads to the rupture and degradation of complex enzyme microcapsules, releases with strong catalytic action
Organized enzyme, under the catalytic action of urase, hydrolysis of urea CO2、NH3、H2O, calcium formate and CO2Reaction generates CaCO3Precipitation knot
Crystalline substance, the formic acid generated, by hydrogenlyase and NAD+(oxidized nicotinamide adenine dinucleotide) catalysis releases more
CO2, after a series of chemical reaction, crack is finally by CaCO3Crystal blocks healing again, reaches distress in concrete
The purpose of self-healing.Its reaction equation is as follows：
C2H2O4Ca+CO2+2H2O→CaCO3↓+2HCOOH
(reduced nicotinamide adenine dinucleotide)
Ca(OH)2+CO2→CaCO3↓+H2O
The present invention can assign distress in concrete self-healing capability using self union concrete complex enzyme microencapsulation material, tool
The compound biological enzyme for having high-efficiency catalytic activity is more than 99.5% polyvinyl alcohol etc. with alcoholysis degree using microcapsules granulating technique
Microcapsule wall material, spray-dried technique are processed into a kind of miniature vessel or packing material with polymer wall.Then urine is utilized
Element, calcium formate generate CO under compound enzyme effect2Characteristic so that concrete cracking position is under water or water vapor acting first
The soluble calcium salts such as sour calcium, calcic retarder, calcium hydroxide generate CaCO3Precipitation, mineralising, crystallization block crack, are finally reached
The purpose of distress in concrete self-healing, to prevent the formation in harmful ion infiltration shortcut channel.
The material of the present invention is prepared as the mixing material with the microcapsules and other powders of mobility, easy to use,
It disposably measures and is mixed in concrete in production Concrete.
Review biological enzyme is uniformly wrapped up under the protection of microcapsules by concrete material, micro- when concrete cracks
Capsule is likely to occur rupture, even if microcapsules do not rupture, polyvinyl alcohol of the alcoholysis degree more than 99.5% can also be micro-
It degrades rapidly under the action of biology and water, general degradation speed is degradation 75% in 46 days, and active life is released after microcapsules rupture
The hydrolysis of object enzymatic into urea releases CO2, under the action of permeating water, free calcium ion will generate CaCO3Precipitation.
The concrete for having used this self union concrete complex enzyme microencapsulation material, can make in the presence of water
The crack self-healing of concrete, to improve the durability of concrete.
Description of the drawings
Fig. 1 is present invention process schematic diagram.
Specific implementation mode
In order to enable those skilled in the art to be further understood that the feature and technology contents of the present invention, please referring to following has
Close detailed description of the invention.
Embodiment 1
Urase 1%, hydrogenlyase 1%, NAD+(oxidized nicotinamide adenine dinucleotide) 1%, PVA alcoholysis degrees are big
In 99.5% polyvinyl alcohol 0.3%, urea 24%, calcium formate 52%, calcic retarder 5% and silicon ash 15.7%, by following
It is prepared by step：
(1) dispensing；
(2) urase, hydrogenlyase, oxidized nicotinamide adenine dinucleotide and polyvinyl alcohol is first dry through spraying
Drying process is processed into microcapsules；
(3) obtained microcapsules are mixed with other components.
Complex enzyme microencapsulation material sample code name EM1 obtained.
Wherein calcic retarder selects the calcium gluconate of dry powder doses.
Embodiment 2
Urase 0.5%, hydrogenlyase 0.5%, NAD+(oxidized nicotinamide adenine dinucleotide) 1%, PVA (alcohol
Xie Du be more than 99.5% polyvinyl alcohol) 0.3%, urea 20%, calcium formate 45%, calcic retarder 5%, silicon ash 27.7%,
It prepares according to the following steps：
(1) dispensing；
(2) urase, hydrogenlyase, oxidized nicotinamide adenine dinucleotide and polyvinyl alcohol is first dry through spraying
Drying process is processed into microcapsules；
(3) obtained microcapsules are mixed with other components.
Complex enzyme microencapsulation material sample code name EM2 obtained.
Wherein calcic retarder selects the calcium citrate of dry powder doses.
Embodiment 3
Sample EM1, EM2 of embodiment 1,2 gained of embodiment are incorporated into concrete respectively, general volume is gelling material
Expect the 0.8~2.0% of weight, carries out crack self-healing experiment and (press《Cementitious capillary waterproofing material》(GB18445—
2001) step in specification carries out), it is analyzed as follows：
Table 1 tests match ratio
Wherein, C35 is strength grade of concrete, and C35 groups are blank sample, and C35-FMK1 groups or C35-FMK2 groups are to refer to
FMK1 or FMK2 is mixed with into the concrete of C35 strength grades.
2 properties of hardened concrete test result of table
Wherein, C35 is strength grade of concrete, and C35 groups are blank sample, and C35-FMK1 groups or C35-FMK2 groups are to refer to
FMK1 or FMK2 is mixed with into the concrete of C35 strength grades.
It may determine that by concrete performance test result, normal concrete impermeability and impervious recovery rate are relatively low, no
With crack self-healing ability.And it can be with mixed with the concrete secondary impermeability pressure of self union concrete complex enzyme microencapsulation material
Restore to original level, there is crack self-healing ability.
But the foregoing is merely the preferable possible embodiments of the present invention, not to limit to the scope of the claims of the present invention, therefore
It is all to change with equivalent structure made by present specification, similarly within the scope of the present invention.
Claims (4)
1. a kind of self union concrete complex enzyme microencapsulation material, it is characterised in that：Component containing following weight percent, urea
Enzyme 0.5~1%, hydrogenlyase 0.5~1%, oxidized nicotinamide adenine dinucleotide 0.5~1%, alcoholysis degree are more than
99.5% polyvinyl alcohol 0.05~0.3%, urea 18~24%, calcium formate 39~52%, calcic retarder 5~10% and silicon
Ash 10~30%, wherein urase, hydrogenlyase, oxidized nicotinamide adenine dinucleotide and polyvinyl alcohol are first through spraying
Drying process is processed into microcapsules and is mixed again with other components.
2. self union concrete complex enzyme microencapsulation material according to claim 1, it is characterised in that：The urea and first
Sour calcium powder be broken into it is powdered, and in molar ratio be about 1：1 is uniformly mixed.
3. self union concrete complex enzyme microencapsulation material according to claim 1, it is characterised in that：The calcic slow setting
One kind in sugar calcium of the agent selected from dry powder doses, calcium gluconate, calcium citrate, calcium tartrate, wooden calcium sulfonate.
4. by the preparation method of any self union concrete complex enzyme microencapsulation material of claims 1 to 3, feature exists
In including the following steps：
(1) dispensing；
(2) by urase, hydrogenlyase, oxidized nicotinamide adenine dinucleotide, with the first spray-dried work of polyvinyl alcohol
Skill is processed into microcapsules；
(3) obtained microcapsules are mixed with other components.
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Cited By (3)
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| CN112209691A (en) * | 2020-09-04 | 2021-01-12 | 苏州良浦天路新型建材有限公司 | Ash aerated block and preparation method thereof |
| WO2023039274A1 (en) * | 2021-09-13 | 2023-03-16 | Worcester Polytechnic Institute | Enzymatic construction material |
| CN118666542A (en) * | 2024-08-26 | 2024-09-20 | 西南石油大学 | Enzymatic self-healing concrete and preparation method thereof |
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| CN118666542A (en) * | 2024-08-26 | 2024-09-20 | 西南石油大学 | Enzymatic self-healing concrete and preparation method thereof |
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| CN108558260B (en) | 2020-12-01 |
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