CN109809728A - Cement composite material comprising surface modified silicon crack autogenous healing capsule and its manufacturing method - Google Patents
Cement composite material comprising surface modified silicon crack autogenous healing capsule and its manufacturing method Download PDFInfo
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- CN109809728A CN109809728A CN201811337689.1A CN201811337689A CN109809728A CN 109809728 A CN109809728 A CN 109809728A CN 201811337689 A CN201811337689 A CN 201811337689A CN 109809728 A CN109809728 A CN 109809728A
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- capsule
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Abstract
The present invention relates to a kind of crack autogenous healing capsules, without other catalyst, just can directly be mixed in realizes encapsulated cement composite material using nucleation material, the nucleation material include be mixed with can with the inorganic volcanic ash class reaction bonded material of the free calcium ion or calcium hydroxide hydrate reaction for including in cement composite material and the silicon crystal of modification；The shortcomings that the invention further relates to a kind of capsule preparation method thereof, this method does not need other catalysts, avoids the original selfreparing capsule for using organic nucleation material, it is outstanding that crack reinforces efficiency.
Description
Technical field
Present embodiment is related to a kind of crack autogenous healing capsule, without other catalyst, just can directly be mixed in use
Nucleation material realizes encapsulated cement composite material, the nucleation material include be mixed with can in cement composite material
The inorganic volcanic ash class reaction bonded material of the free calcium ion or calcium hydroxide hydrate reaction that include and the silicon wafer of modification
Body；Present embodiment is related to a kind of capsule preparation method thereof, and this method does not need other catalysts, avoids original use
The shortcomings that selfreparing capsule of organic nucleation material, it is outstanding that crack reinforces efficiency.
Background technique
The cement composite material of selfreparing capsule is mixed with when crack occurs, capsules break, the nucleation material of capsule
Crack portion is arrived in material dissolution, can not only save maintenance management expense with self-healing crack, and have for maintenance management and
It is difficult to put into the works or hazard space of manpower, also the advantages of the maintenance of crack easy to accomplish.It, can be in selfreparing capsule
A large amount of self-repair materials comprising can directly safeguard crack, i.e. nucleation material, thus have and can split in damage location
The advantages of seam happening part selectively reacts.The nucleation material of previous selfreparing capsule largely uses organic both at home and abroad
Material.For organic-based material compared with mineral-type materials, the reaction time is fast, has the advantages that be easy encapsulated.Mineral-type materials with
The reaction time of organic-based material is compared, and has the shortcomings that relatively slow mineral-type materials capsule needed for repairing there are crack
Change difficult disadvantage.Mineral-type materials are due to being the material with cement composite material homologous series, thus characteristic is identical, and having can
The advantages of increasing crack restoring area, that is, maintenance position durability, when nucleation material outflow, replace other catalyst and
By means of invading the moisture of cement composite inner, can simply induced reaction, thus studied recently.But
So far, using the example of mineral-type materials, research case both domestic and external is less, and practical application is few.Especially it is being not present
The place of moisture there are problems that being difficult to react, and since the reaction time is long, so far, organic-based material still occupies advantage.
But organic-based material is in order to be reacted, it is also desirable to catalyst in addition.That is, not in nucleation material together comprising catalysis
Agent, it is required that two kinds of the capsule comprising nucleation material, capsule comprising catalyst etc..Catalyst is common material, thus
Capsule comprising catalyst does not refer to especially.But organic-based material is necessarily required to the catalysts for reaction.In other words
It says, even if organic nucleation material flows out to crack portion, the nucleation material that can not be met with catalyst can not be reacted, and not sent out
It is raw to repair reaction.
For foreign technology related to this, classic technology is to come epoxies organic material as nucleation material
Capsule is prepared, other catalyst is made to realize encapsulated and apply.For domestic technique, catalyst is not added separately, but
Develop the capsule of the nucleation material comprising reacting with sunlight (UV).But this can not also be lured in the place of not sunlight
Reaction is led, haves the shortcomings that repair difficult.If comprehensively examining or check advanced technology, when crack occurs, capsules break makes to be nucleated
Material flows out to crack portion, in order to make the nucleation material of outflow react, it is necessary to separately add catalyst or need for anti-
The medium answered.In addition, even if addition catalyst, the region of no catalyst is placed under the difficult environment of reaction, be not catalyzed
In the case where agent, when utilizing reaction material, when being reacted by sunlight, there is also can not react if without sunlight
The shortcomings that.Therefore, it is necessary to a kind of performances not to be situated between by as the presence or absence of organic material nucleation material greatest problem catalyst and reaction
The solution of matter constraint.
[existing technical literature]
[patent document]
The authorization of (patent document 1) Korean Patent the 10-1168038th
Summary of the invention
[the technical problem to be solved in the present invention]
The present invention is precisely in order to solving described problem and researching and developing, and its purpose is to provide a kind of with easy reaction system
The capsule of system, using the nucleation material comprising modified silicon, the modified silicon is that mixing can be necessary with cement composite material inside
The inorganic volcanic ash class reaction bonded material of existing free calcium ion or calcium hydroxide hydrate reaction and be modified, protrude
The advantages of machine material, so that performance is not by the addition of other catalysts and the constraint of reaction medium.
Technical solution
The cement composite material crack autogenous healing capsule of embodiment of the present invention may include: silicon；Nucleation material, phase
For 100 parts by weight of silicon, 1~50 parts by weight of inorganic volcanic ash class material of You Nengyu calcium ion reaction and the silicon
Grain mixing；And the coat of the outer peripheral surface coating in the nucleation material.
The cement composite material of the invention uses crack autogenous healing capsule to be characterized in that: further including by as water solubility
The auxiliary material for promoting to react that the silicon powder or reactive silicon material of silica are constituted, the inorganic volcanic ash class material
Material is aluminum sulfate (Al2(SO4)3), aluminum potassium sulfate (AlK (SO4)2), sodium aluminate (Al2O3nNa2O) independent or mixed form.
More specifically, inorganic volcanic ash class material can be by water-soluble inorganic class gel material, with cementitious composite
The free calcium ion and calcium hydroxide hydrate reaction of material and reach target.Furthermore it is possible to can promote to react by mixing
Auxiliary material and prepare.
Water-soluble inorganic class gel material can be aluminum sulfate (Al2(SO4)3), aluminum potassium sulfate (AlK (SO4)2), sodium aluminate
(Al2O3nNa2O) independent or mixed form may be constructed 50~80 relative to 100 parts by weight of inorganic volcanic ash class material
Parts by weight.Auxiliary material for promoting reaction is will be as the silicon powder or reactive silicon material furthermore of water soluble silica
Material, relative to 100 parts by weight of inorganic volcanic ash class material, the form mixed by 20~50 parts by weight.In addition, anti-in order to adjust
Speed is answered, the fluorine class delayed-action activator (KFnH of 1~5 parts by weight can be in addition added2O)。
Inorganic volcanic ash class material with silicon by mixing and modified step, when modified silicon is used as nucleation material,
It meets and can react with free calcium ion or calcium hydroxide hydrate, can solve because catalysts and reaction medium cause
The above problem.
It is as follows that reaction mechanism is repaired into the crack that encapsulated modified silicon is used as the selfreparing capsule of nucleation material.It splits
The capsule for stitching and rupturing, modified silicon flow out to inside crack, can reach two kinds of reactions.The first reaction is, as modified silicon
Sulfate ion (the SO of one of main component4 2-) and aluminium ion (Al3+) and calcium ion (Ca) and moisture (H2O it) meets, generates and make
For the ettringite of hydrate, it is formed in the acicular substance that crosslinked action is played the role of in crack portion, silicon plays adhesive or filler,
Repair crack portion, i.e. maintenance crack.Second of reaction is that sodium ion (Na), potassium (K) ion and internal calcium phase are met, and is passed through
Silicates reaction product repairs crack portion, furthermore it is possible to induce original not hydrated cementitious and calcium hydroxide hydrate
Secondary hydration reaction can be such that crack firmly repairs.It is therefore not necessary to the constraint item that other catalyst or reaction medium require
Part, can be so that reaction efficiency realizes maximization.
The preparation method of the cement composite material crack autogenous healing capsule of embodiment of the present invention may include: preparation energy
The step of inorganic volcanic ash class material reacted with calcium ion；The inorganic volcanic ash class material is mixed with silicon and makes silicon
Modified step；
The silicon of the modification is set to realize encapsulated step；And in the encapsulated capsule outer peripheral surface coating coat
Step.
[beneficial effect]
The crack autogenous healing capsule of the cement composite material comprising modified silicon of embodiment of the present invention, using including modification
The nucleation material of silicon, the modified silicon are that mixing can be with the free calcium ion and calcium hydroxide water that include in cement composite material
It closes the inorganic volcanic ash class material of object reaction and is modified, can be reacted without adding other catalysts and medium just,
Thus it is capable of increasing the remediation efficiency of nucleation material.In addition, generating by means of inorganic volcanic ash class material and being used as ordinary cement
The needle-shaped ettringite of composite material hydrate, by facilitate restore alkalinity silicates reaction product and silicon bonding and
Filling effect, can firmly self-maintain fracture surface, thus the selfreparing capsule of the invention with this composition not only may be used
To be applied to surface as coating agent, it can be also directly mixed in cement composite material, about 3-10mm water is covered in works
It is flat or its more than, be constructed into the film form with thickness to a certain degree, or construct as works parent itself.
Detailed description of the invention
Fig. 1 is the figure for showing the first reaction mechanism for reaching modified silicon of the invention.
Fig. 2 is the figure for showing the second reaction mechanism for reaching modified silicon of the invention.
Fig. 3 is the figure for being shown schematically as foreign technology.
Fig. 4 is the figure for being shown schematically as domestic technique.
Fig. 5 is to be shown schematically as figure of the invention.
Fig. 6 is the flow chart for showing the preparation method of capsule of the invention.
Fig. 7 is the exemplary figure for being shown schematically as preparing through the invention.
Fig. 8 shows the skeleton diagram using the solution of the present invention.
Specific embodiment
Illustrate a part of the embodiments of the present invention by exemplary drawings following for the convenience of explanation.To each figure
In terms of constituent element records appended drawing reference, for identical constituent element, even if being shown on different figures, also identify as far as possible
For identical label.
Term or word used in present specification and claims is not limited to common or dictionary meaning, stands
Inventor is enough in order to illustrate the invention of itself with the best approach and can suitably define the principle of the concept of term, should only be explained
For the meaning and concept being consistent with technical idea of the invention.In addition, in terms of the constituent element for illustrating the embodiment of the present invention,
The terms such as first, second, A, B, (a), (b) can be used.This term is served only for this composition element being different from other compositions
Element, essence or order or sequence of corresponding constituent element etc. are not limited by the term." connect when being recorded as certain constituent element
Connect " or " in conjunction with " when another constituent element, it is thus understood that this composition element both can be directly connected to or be incorporated into another structure
At element, " connection " or " in conjunction with " can also be gone back between this composition element and another constituent element has other constituent elements.
Therefore, what is illustrated in the embodiment and figure recorded in this specification constitutes most preferably implementation only of the invention
Example, and it is not all represent technical idea of the invention, thus be interpreted as at the application time point, can have can substitute them
Various equipollent and variation.In addition, omitting the known function and composition for may not be necessary obscuring main idea of the present invention
It is described in detail.
The cement composite material crack autogenous healing capsule of the embodiment of the present invention may include: silicon；Nucleation material, it is opposite
In 100 parts by weight of silicon, 1~50 parts by weight of inorganic volcanic ash class material of You Nengyu calcium ion reaction and the silicon particle
Mixing；In the coat that the outer peripheral surface of the nucleation material coats.
Inorganic volcanic ash class material can free calcium by water-soluble inorganic class gel material, with cement composite material
Ion and calcium hydroxide hydrate reaction and reach target.Furthermore it is possible to which the auxiliary material of reaction can be promoted by mixing
Preparation.Water-soluble inorganic class gel material can be for by aluminum sulfate (Al2(SO4)3), aluminum potassium sulfate (AlK (SO4)2), sodium aluminate
(Al2O3nNa2O) independent or mixed form may be constructed 50~80 relative to 100 parts by weight of inorganic volcanic ash class material
Parts by weight.Auxiliary material for promoting reaction is will be as the silicon powder or reactive silicon material furthermore of water soluble silica
Material, relative to 100 parts by weight of inorganic volcanic ash class material, the form mixed by 20~50 parts by weight.In addition, anti-in order to adjust
Speed is answered, the fluorine class delayed-action activator (KFnH of 1~5 parts by weight is in addition added2O)。
Reaction mechanism is repaired in the crack that modified silicon is used as the selfreparing capsule of nucleation material to illustrate in fig. 1 and 2.Figure
1 is the sulfate ion (SO as one of modified silicon main component4 2-) and aluminium ion (Al3+) and calcium ion (Ca) and moisture
(H2O it) meets, generates the ettringite as hydrate, be formed in the acicular substance that crack portion plays crosslinked action, silicon plays viscous
Mixture or filler effect, make crack portion heal, i.e. maintenance crack.Fig. 2 is sodium ion (Na), potassium in modified silicon main component
(K) ion and internal calcium phase are met, and by silicates reaction product, so that crack portion is healed, in addition can be induced original
Not hydrated cementitious and calcium hydroxide hydrate secondary hydration reaction, can make crack firmly heal.It is therefore not necessary to other
The constraint condition that catalyst or reaction medium require, can be so that reaction efficiency maximizes.In addition, by strong basic ion,
It can add and obtain the performance that alkalinity is restored in the inside for making neutralisation.
In general, the ingredient of cement includes tricalcium silicate (3CaOSiO2) and dicalcium silicate (2CaOSiO2) constitute,
Since there are calcium ions abundant, thus the nucleation material that can directly react with this calcium ion is proposed in the present invention.This
Kind of nucleation material can carry out encapsulated, if capsules break, modified silicon nucleation material is not necessarily to other catalyst, can
It reacts and solidifies with the calcium ion of cement composite material.
But if examining or check similar techniques related to this, representative foreign technology is roughly illustrated in Fig. 3.
In addition to selfreparing capsule, answer as shown in figure 3, need to only make other catalyst carry out encapsulated and be applied to cementitious composite together
Material, even if organic nucleation material flows out to crack portion, the nucleation material that can not be met with catalyst can not also react, and not send out
It is raw to repair reaction.In addition, the intensity of capsule itself is weak, it is difficult to mix application together with cement composite material.Due to this reason,
Capsule and catalyst are mixed in epoxies basic material, form film coating on surface.Therefore, if only splitting with scratch grade
Seam is object, then for the crack extended inward, healing effect is limited.
Fig. 4 roughly illustrates representative domestic technique.Domestic technique is in order to make up the other catalysis of foreign technology
Agent problem, nucleation material use the material only reacted using sunlight (UV).But in this case, there is also do not having
Have and is difficult to the shortcomings that inducing healing reaction in the space of sunlight.In addition, the intensity of capsule itself is weak as foreign technology,
The level of thin film coating is only formed on surface.
The capsule technique of the invention for using modified silicon as nucleation material is roughly illustrated in Fig. 5.Modified silicon is used
In making up the problem of original nucleation material is reacted, without using other catalyst, the conditional variable of such as sunlight can solve
Caused influence.In addition, having the advantages that directly be mixed in cement composite material by the reinforcing to film, can make to damage
Vector, which is realized, to be minimized.
The selfreparing capsule preparation side of nucleation material will be used as with the modified silicon of the reaction mechanism by illustrating in Fig. 6
Method.Modified silicon can by capsule be melted into have can with outside partition film in the form of and protected.At this point, film can be by urea
(urea) the ureaformaldehyde material synthesized with formaldehyde (formaldehyde), but it is not limited to this.It is encapsulated to pass through original position
(In-situ) polymerization is realized, the size of capsule can be adjusted according to RPM.
In the outer peripheral surface for the capsule being thusly-formed, coat could be formed with.Coat can use coating liquid, multiple layer
Folded coating.
Repeatedly coating is executed as described above and is made the reasons why coat is laminated in nucleation material, is in order to of the invention
For capsule during being matched with cement composite material, control leads to nucleation material exposure etc. due to the friction etc. formed with other
The low factor of durability.
Various material such as polymer, ceramics can be used in the coating liquid, in order in engagement process, so that of the invention
Capsule cooperation should use the material of expression given strength.That is, due to directly being mixed with cement composite material, thus it is directed to cement
The constituent material and mixer of composite material apply the pressure such as friction and shearing, it is thus possible to carry out loss amount with minimizing more
Secondary coating, thus, it is possible to improve the moisture blocked force to nucleation material.
Specifically, coating liquid may include TEOS (tetraethyl orthosilicate, ethyl orthosilicate), by
This, can form coat on the surface of the capsule.TEOS in order at one layer of surface overbrushing, can be used sodium dihydrogen phosphate,
Ammonium chloride, TBAF (tetrabutylammonium fluoride, tetrabutyl ammonium fluoride) solution, distilled water etc. are as construction ring
Bottoming needed for border (base) agent.I.e., it is possible to which encapsulated TEOS is added in this bottoming agent, is realized and coated by blender.
Fig. 7 shows the example prepared through the invention.
Modified silicon of the invention is used as to the selfreparing capsule of nucleation material, can directly be mixed with cement composite material.
Therefore, it can use as shown in Figure 8.Different from being only used as original capsule of thin film coated material, the present invention not only can be with original
There is capsule to be used as thin film coated material in the same manner, cement composite material can also be mixed in, is used as 3mm or more 30mm quilt below
Cover material.Alternatively, it is also possible to be applied in the critical section of new construction object comprehensively or locally.
More than, all constituent elements for just constituting the embodiment of the present invention are combined into one or are combined together the situation of utilization
It is illustrated, but simultaneously non-present invention is necessarily limited to this embodiment.As long as that is, owning within the scope of the object of the invention
Constituent element also combines to the property of can choose more than one utilization.In addition, the arts such as " comprising " " composition " " having " recorded above
Language, as long as no especially opposite record, meaning can contain corresponding constituent element, thus and other non-excluded constituent elements,
It should be interpreted that can also include other constituent elements.All terms including technical or scientific terms, as long as not
It defines together, then there is meaning identical with the content that those skilled in the art are commonly understood by.Such as word
The term that the term that allusion quotation defines generally uses like that should be interpreted that the meaning on the unity and coherence in writing with the relevant technologies is consistent, as long as at this
It is not exactly defined in invention, must not excessively or exceedingly be construed to formal meaning.
Above illustrates only exemplary illustration technical idea of the invention, as long as the technical field of the invention
Technical staff just it will be appreciated that in the range of without departing from intrinsic propesties of the present invention, various revision and deformation can be carried out.Cause
This, embodiment disclosed in the present invention, which is not for limiting but for, illustrates technical idea of the invention, and non-present invention
Technical idea range is limited by this embodiment.Protection scope of the present invention should be solved according to following claims
It releases, all technical ideas in equivalents, which should be interpreted that, therewith is contained in interest field of the invention.
Claims (3)
1. a kind of cement composite material crack autogenous healing capsule, comprising:
Silicon；
Nucleation material, relative to 100 parts by weight of silicon, the inorganic volcanic ash class material 1 that You Nengyu calcium ion reacts~
50 parts by weight are mixed with the silicon particle；And
In the coat that the outer peripheral surface of the nucleation material coats.
2. cement composite material according to claim 1 crack autogenous healing capsule, which is characterized in that
It further includes by the silicon powder or reactivity as water soluble silica that the cement composite material, which uses crack autogenous healing capsule,
The auxiliary material for promoting to react that silicon materials are constituted,
The inorganic volcanic ash class material is aluminum sulfate (Al2(SO4)3), aluminum potassium sulfate (AlK (SO4)2), sodium aluminate
(Al2O3nNa2O) independent or mixed form.
3. a kind of cement composite material preparation method of crack autogenous healing capsule, comprising:
The step of preparing the inorganic volcanic ash class material that can be reacted with calcium ion；
The step of inorganic volcanic ash class material is mixed with silicon and makes Si modification；
The silicon of the modification is set to realize encapsulated step；And
In the step of encapsulated capsule outer peripheral surface coats coat.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0155451 | 2017-11-21 | ||
| KR20170155451 | 2017-11-21 | ||
| KR10-2018-0098279 | 2017-11-21 | ||
| KR1020180098279A KR20190058276A (en) | 2017-11-21 | 2018-08-23 | Self-healing capsule with surface modified silicon and manufacturing method the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109809728A true CN109809728A (en) | 2019-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811337689.1A Pending CN109809728A (en) | 2017-11-21 | 2018-11-12 | Cement composite material comprising surface modified silicon crack autogenous healing capsule and its manufacturing method |
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| CN (1) | CN109809728A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510910A (en) * | 2019-09-26 | 2019-11-29 | 交通运输部公路科学研究所 | A kind of thin micro crack microcapsules self-repair material of the concrete that cyst wall is degradable |
| CN111333359A (en) * | 2020-02-28 | 2020-06-26 | 河海大学 | Concrete self-repairing system with self-adaptive seal heads |
| WO2021008341A1 (en) * | 2019-07-18 | 2021-01-21 | 华南理工大学 | Cement-based material crack self-repairing agent capable of curing corrosive sea water ions, and preparation method therefor and application thereof |
-
2018
- 2018-11-12 CN CN201811337689.1A patent/CN109809728A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021008341A1 (en) * | 2019-07-18 | 2021-01-21 | 华南理工大学 | Cement-based material crack self-repairing agent capable of curing corrosive sea water ions, and preparation method therefor and application thereof |
| CN110510910A (en) * | 2019-09-26 | 2019-11-29 | 交通运输部公路科学研究所 | A kind of thin micro crack microcapsules self-repair material of the concrete that cyst wall is degradable |
| CN111333359A (en) * | 2020-02-28 | 2020-06-26 | 河海大学 | Concrete self-repairing system with self-adaptive seal heads |
| CN111333359B (en) * | 2020-02-28 | 2021-04-09 | 河海大学 | Concrete self-repairing system with self-adaptive seal heads |
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Application publication date: 20190528 |