CN106064916A - Ultrafine powder contains curing materials and the curing of thing - Google Patents
Ultrafine powder contains curing materials and the curing of thing Download PDFInfo
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- CN106064916A CN106064916A CN201610364877.8A CN201610364877A CN106064916A CN 106064916 A CN106064916 A CN 106064916A CN 201610364877 A CN201610364877 A CN 201610364877A CN 106064916 A CN106064916 A CN 106064916A
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- Prior art keywords
- curing materials
- thing
- hardening
- curing
- agent
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Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The present application aims to provide curing materials and the curing thereof that a kind of ultrafine powder contains thing, and this curing materials can obtain, in the case of the mixing thing solidification making warp-wise ultrafine powder contain suitably to add water in thing and modulated, the firming body that hydrophobicity is excellent.This curing materials is made up of ultrafine powder or ultrafine powder based on it contains in thing (treated object) and makes it solidify for adding to be mixed into.This curing materials is to be made up of the host constituted with cement (inorganic bond) and the secondary agent containing hydrophobicity-imparting agent.Hydrophobicity-imparting agent suitably contains other silane compounds such as reactive silicone oil, alkoxysilane in moisture-curable type silicone oligomer.
Description
Technical field
The present invention relates to a kind of curing materials and use the curing of this curing materials, this curing materials is used for adding
It is mixed into the super of the mud etc. that is made up of or with this ultrafine powder as constituent the ultrafine powder of colloidal solid composition etc.
Powder body contains in thing (treated object) so that it is solidification.
In this specification, so-called ultrafine powder refers to that the aggregation of the particle of below a few micrometers (refers to chemistry engineering
Association compile " chemistry engineering dictionary " (Showa on May 30th, 49) ball kind, page 410 " pulverizer " one).It addition, in ultrafine powder,
Do not contain only particle possibly together with the fibrous material below a few micrometers such as asbestos.
Mud that so-called mud etc. are not limited to be accumulated with the bottom of pond, river and ocean etc., clay, containing organic
The mud that ultrafine powder is constituent (muddy treated object) of the peat of thing, sapropel etc..In mud etc., containing producing
State be ultrafine powder or mince based on the mud of its agglutinator, wall mud, Rock Powder, laterite, coal ash, slag, slag,
Burning ash, even pigment etc..
Background technology
Mud etc. with harmful ultrafine powder (volcanic ash, coal ash, mineral powder, coal smoke, asbestos dust etc.) are
Constituent is the most containing harmful heavy metal class (such as, Cr (VI) Cd, Hg, Pb, As etc.).
In order to solidify the mud etc. in building, building trade, with the solidification of the earth etc. using inorganic system binding agent cement
The relevant technology of material has multiple motion in patent documentation 1~13 etc. and is just being practiced.
These technology are used for following purpose.To soil reinforcement, make removing of the mud etc. occurred in building/building construction process
Fortune facilitation, prevent sewage in carrying from flowing out from mud, disperse etc. while, prevent in construction earth due to rainwater or river
Rise and outflow etc..
The technology that the curing materials of mud etc. described in above-mentioned patent documentation 1~13 is relevant, with the present application not
With, the most energetically for the purpose of hydrophobic property, certainly, not contain silicone sclerosing agent or even hardening thing and compose as hydrophobicity
Give agent, the patentability of the present application is not affected.In this specification, " or even " it is the statement to institute's how, such as,
" silicone sclerosing agent or even hardening thing " mean this scope from silicone sclerosing agent to hardening thing, the most such as, hereinafter will mention
" hydrophobicity or even unwetted " means from this scope of hydrophobicity to unwetted.
It addition, in patent documentation 14, propose have one " to combine raw containing nonionic surfactant and silicone-containing
Becoming the vinyl alcohol system polymer of side chain, cobaltous chloride (II) and the salt of ammonium salt " the hardening aid composition that forms (refers to description
Summary etc.).
But, the silicone (organo-silicon compound) in this hardening aid composition is for by mixing with cement composition
Obtain the compositions of the firming body (hardenite) of high intensity and unwetted, the patentability of the present application be there is no impact.
It addition, its main chain of silicone in the present application is " siloxanes that side chain is methyl or phenyl ".
Comparatively speaking, the vinyl alcohol system polymer in the document has siloxanes and combines generation side chain, and hardening thing (solidifies
Body) partly there is siloxanes combination, main chain only " has the polyethylene of OH base or acetate groups " in side chain.Therefore,
It is believed that add " there is siloxanes and combine the vinyl alcohol system polymer of generation side chain " in patent documentation 14 to " cement "
In, even if adding cobaltous chloride, alkaline metal salt/basic carbonate etc. again, can not realize the present application hydrophobicity or even
Unwetted (low water absorption).Incidentally, for SP value (solubility parameter), the SP value of polyvinyl alcohol is 12.60, and phase
Over the ground, the SP value of dimethyl siloxane is that 7.3 (the SP value of polyethylene is 7.9) (refer to Japanese bonding association and compile " bonding handbook
(second edition) " (clear 55-11-10) page 110).
Therefore, the patentability of the present application also, as patent documentation 1~13, is not affected by patent documentation 14.
Although additionally, the curing materials of patent documentation 1~14 being added mud etc. to and the firming body (hardenite) that obtains
All obtain intensity (compressive strength), hydrophobicity or even unwetted to a certain degree, but as firming body water-fast in crumble
Property (resistance to mud again) not among anticipated, and the elution of the harmful substances such as harmful heavy metal class suppression is the most unexpected.
Prior art literature
Patent documentation
Patent documentation 1:H7-136693 patent gazette
Patent documentation 2:H8-071598 patent gazette
Patent documentation 3:JP2000-61424 patent gazette
Patent documentation 4:JP2000-176493 patent gazette
Patent documentation 5:JP2001-182044 patent gazette
Patent documentation 6:JP2002-282894 patent gazette
Patent documentation 7:JP2005-13973 patent gazette
Patent documentation 8:JP2005-131595 patent gazette
Patent documentation 9:JP2006-137840 patent gazette
Patent documentation 10:JP2008-94901 patent gazette
Patent documentation 11:JP2008-55301 patent gazette
Patent documentation 12:JP2009-214083 patent gazette
Patent documentation 13:JP2013-107966 patent gazette
Patent documentation 14:JP2004-210588 patent gazette
Summary of the invention
The problem that invention is to be solved
The present application is the first purpose to provide a kind of curing materials for these reasons, and this curing materials can lead to
Cross make warp-wise ultrafine powder contain in thing add suitable quantity of water modulated mixing thing solidification and obtain the firming body that hydrophobicity is excellent.
Second purpose of the present application is to provide such a curing materials, and this curing materials can obtain having excellent
Good hydrophobicity have again simultaneously high intensity, the characteristic of unwetted thus possess water-fast in crumbling property, and then can suppress harmful
The firming body of heavy metal class elution.
3rd purpose of the present application is to provide such a curing materials, and this curing materials does not relies on existing
The fluororesin being commonly used for hydrophobicity-imparting agent, the organic material of polymer coagulant (patent documentation 2,6 etc.) being commonly used for agglutinant
Material, and it is obtained in that the firming body of the resistance to deterioration possessing tolerance light, heat and lonizing radiation.The means of solution problem
The present application artificially solve the problems referred to above make great efforts develop with keen determination, result contemplate following composition curing materials and
Curing.
The curing materials of the present application is, is mixed into ultrafine powder for interpolation and contains and make it solid in thing (treated object)
Change, by the host constituted with cement (inorganic bonding agent) and containing hydrophobicity-imparting agent and the secondary agent institute structure of hardening adjuvant
The curing materials become.It is characterized in that, described hydrophobicity-imparting agent is by moisture-curable type silicone oligomers (hereinafter referred to as " silicon
Ketone oligomer ".) constitute or based on the silicon-ketone composition of this silicone oligomers.
In the curing materials of the present application, it is preferable that described hardening adjuvant is hardening accelerator, bacillus generation promotion
At least one during Hydraulic binding lowers agent between agent and particle.
It addition, in the curing materials of the present application, it is highly preferred that in the above-described configuration, described hardening accelerator contains
CaCl2, described bacillus generates accelerator and contains CoCl2, between described particle, Hydraulic binding attenuating agent contains citric acid.
The curing materials of the present application is, solidifies, with the curing materials of above-mentioned composition, the side that described ultrafine powder contains thing
Method.It is characterized in that, including following procedures:
(1) contain in thing (treated object) to described ultrafine powder, fit with the silicon-ketone composition of described curing materials simultaneously
Local add water and as the operation of homodisperse slurry;And
(2) add in this slurry and mix the cement of described curing materials as homodisperse mixing thing, and at room temperature
Or make this mixing thing maintenance hardening under low-temperature heat pressurized conditions and as the operation of firming body.
The effect of invention
Hereinafter, the effect of the present application is been described by.
In recent years, the output of the trade wastes such as coal ash, asbestos, Alumina residue, increases, and then waste treatment place
Guarantee there is also the trend of difficultyization.
If using the curing materials of the present application, then need not rely upon and the mud etc. containing these trade wastes is entered
Row waste treatment, so that it may obtain the firming body having valency that can effectively utilize in building, building trade.I other words, this firming body has
Have excellent hydrophobicity have again simultaneously high intensity, the characteristic of unwetted thus possess water-fast in crumbling property, and then can suppress
Harmful substance heavy metal class elutes.
It addition, the firming body obtained to the curing materials of use the present application (carries out powder in the case of non-granular
Broken), the curing materials and the water that again add the present application are modulated;If make under room temperature or low-temperature heat pressurized conditions through
The mixing thing maintenance hardening of modulation, then and then the regeneration firming body of high intensity can be obtained.So, Industry Waste can just be expanded
Gurry mud etc. in building, building trade as the utilization of raw material.
The advantage in production that the manufacture method of the firming body of the present application is had is, to powder bodies such as mud
Containing thing (treated object) adding the curing materials of the present application, adding the mixing thing after appropriate water is modulated again, often carry out
Temperature or low-temperature heat pressurization, make it harden by the method for such simplicity and obtain firming body.
Detailed description of the invention
Hereinafter, embodiments of the present invention are described in detail.It should be pointed out that, unless otherwise prescribed, the following description
" part " and " % " of middle expression unit of fit refers to " mass parts " and " quality % ".
A. the curing materials of the present application contains host, the Yi Jiyou being made up of < (1) cement (inorganic bond) >
< (2) hydrophobicity-imparting agent) > and < 3) hardening adjuvant > constitute secondary agent, suitably contain < (4) other pair agent >.And, firmly
Change at least one that adjuvant contains hardening accelerator, bacillus generates between accelerator and particle in Hydraulic binding attenuating agent.
< (1) cement (inorganic bond) >
As cement (inorganic bond), generally use hydraulic cement (containing latent hydraulicity cement.), but air-setting water
Mud (Gypsum Fibrosum, Calx) also may be used.As hydraulic cement, portland cement (Portland cement) can be enumerated (containing mixing silicic acid
Salt cement.), blast furnace cement.It should be pointed out that, as promoting that congealing reaction etc. also can be to hydraulic cement gaseous mixture hydraulic cement.
Here, cement relative to the mixed proportion of (ultrafine powder contain thing) such as mud due to the kind of mud etc. and close
The water content of degree, mud etc. and cannot limit.With the amount of cement proportionally, firming body intensity (uniaxial compressive strength) and
The trend that in water-fast, crumbling property (resistance to mud again) is improved.
< (2) hydrophobicity-imparting agent (hardening silicon-ketone composition)) >
Here, in silicon-ketone composition, based on silicone, also contain its presoma alkoxy silane etc..
As hydrophobicity-imparting agent, with moisture-curable type silicone oligomers (silicone oligomer) (hereinafter referred to as " silicon
Ketone oligomer ") (I) be necessary, is suitably used silicone oil (II), fluorine-containing organoalkoxysilane (III) or alkoxyl silicone
Alkane (IV), is suitably used the hardening silicone (compositions) containing surfactant (V) simultaneously).It should be pointed out that, that silicone is oligomeric
Thing generally preferably uses and with the addition of hardening catalyst, uses after adding in the case of being not added with hardening catalyst.
(I) silicone oligomers
The preferably partial hydrolysis condensate of the alkoxysilane compound containing trialkylsilyl group in molecular structure represented by formula (1).
R1 X Si(OR2)4-X (1)
But, R1: H or 1 valency alkyl, R2: alkyl, the integer of x:0~3 (preferably 1~3) (it should be pointed out that, R1、R2Identical
Or it is different.).
As above-mentioned R11 valency alkyl, the alkyl of preferably C1~C18, the cycloalkyl of C3~C8, the aryl of C6~C8,
Aralkyl (virtue fat) base of C7~C8.
Specifically, as follows.
Alkyl: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, secondary
Amyl group, hexyl, heptyl, positive octene, iso-octyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, myristyl, ten
Six alkyl, octadecyl;
Cycloalkyl: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group;
Aryl: phenyl, tolyl, xylyl;
Aralkyl: 1-phenylethyl, 2-phenylethyl, adjacent methyl-benzyl, a methyl-benzyl, to methyl-benzyl.
Above-mentioned 1 valency alkyl is that hydrogen atom also may be used by what functional group's (reactive group) had replaced.As functional group, halogen can be enumerated
Atom (such as, chlorine, fluorine, bromine and iodine etc.), hydroxyl, cyano group, amino, carboxyl etc..These functional groups and ultrafine powder particle or even
Cement constituent (Calx, clay) reaction bonded is expected to improve hydrophobic persistence.
R2Alkyl be preferably the alkyl of C1~C4.Concrete base name can be enumerated in aforementioned C1~C18 as C1~C4
Illustrate.
As aforementioned alkoxy silane, specifically, MTMS, MTES, first can be enumerated
Base three isopropoxy silane, phenyltrimethoxysila,e, ethyl trimethoxy silane, propyl trimethoxy silicane, diphenyl two
Methoxy silane, phenyl methyl dimethoxysilane, tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, four fourths
TMOS or its mixture.
As the commercially available product of the silicone oligomers containing hardening catalyst, can enumerate " KR-251 ", " KR-400 " (more than
For SHIN-ETSU HANTOTAI's silicone (strain) trade name processed).They can be used together and latex with surfactant.
As the commercially available product of the silicone oligomers without hardening catalyst, include, for example " KR-242 ", " KR-500 ",
" KR-213 ", " KC-89 " (being SHIN-ETSU HANTOTAI's silicone (strain) trade name processed above) etc..
Additionally, also use the commercially available product containing the hardening catalyst silicone oligomers that latex (hydrosol) has been changed the most again
Can.As commercially available product, " SILRES BS SMK 2101J ", " SILRES BC 2103 " can be enumerated (above for Asahi Chemical Industry
WACKER silicone (strain) trade name processed) etc..
It addition, " SILRES BS POWDER A " (Asahi Chemical Industry as the commercially available product of powder of silicone oligomers, can be enumerated
WACKER silicone (strain) trade name processed).They once contact with water generation dealcoholization and become silicone hardening thing, generally not
Coordinate under the state of hardening.
It should be pointed out that, that above-mentioned silicone hardening thing (powder) can use with silicone oligomers simultaneously.As this silicone hardening thing
Commercially available product, " KMP-590 ", " KMP-701 ", " X52-854 ", " X52-1621 " can be enumerated (above for SHIN-ETSU HANTOTAI's silicone (strain)
Trade name processed) etc..
Above-mentioned each silicone oligomers is (except silicone hardening thing.) in the case of in advance without hardening catalyst, add hardening
Catalyst.
In the case of individually making cement effect with silicone oligomers, the use level of silicone oligomers is, it is preferable that relative to
Cement 100 parts is less than 10 parts, it is highly preferred that be less than 5 parts.If silicone is superfluous, then the intensity of firming body may be produced not
Good impact.
As hardening catalyst, and indefinite.Such as, can be listed below organo-metallic compound, mineral acid, organic acid,
Inorganic base, amine.Wherein, preferred organo-metallic compound.Relative to the addition of hardening catalyst silicone oligomers, according to urging
The kind of agent, the kind etc. of silicone oligomers and different.Generally, relative to silicone oligomers 100 parts, hardening catalyst is 1
~15 parts.
(1) organo-metallic compound
Organotin system: dibutyltin diacetate, octanoic acid dibutyl tin, dibutyl tin laurate etc.;
Organo-aluminium system: aluminium tris(acetylacetonate), three (ethyl acetoacetate) aluminum, diisopropoxy (ethyl acetate) aluminum
Deng;
Organic zirconium system: (acetylacetone,2,4-pentanedione) zirconium, tri acetylacetonato zirconium, four (glycol monoethyl ether) zirconium, four (ethylene glycol lists
Butyl ether) zirconium etc.;
Organic titanium system: four (glycol monoethyl ether) titanium, four (ethylene glycol monoethyl ether) titanium, four (ethylene glycol monobutyl ethers) etc..
(2) mineral acid
Hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid etc.;
(3) organic acid
Formic acid, acetic acid, oxalic acid, trifluoroacetic acid etc.;
(4) inorganic base
Ammonia, sodium hydroxide, potassium hydroxide etc.;
(5) amine (containing derivant)
Ethylenediamine, alkanolamine, amino modified silicone, amino silane, silazane etc..
As the commercially available product of organo-metallic compound, can enumerate " D-20 " as titanium system, as zinc system " D-15 ",
" CAT-AC " (being SHIN-ETSU HANTOTAI's silicone (strain) trade name processed above) as aluminum system etc..
(II) silicone oil:
Exist the non-reacted silicone oil represented by following formula (2), (3) or (4) and following formula (5), (6),
(7), the reactive silicone oil represented by (8) and (9).Wherein, preferred reactive silicone oil.It should be pointed out that, following each chemistry
In formula, the scope of m, n does not limit.The scope of m, n is shown as (the 20 DEG C of dynamic viscosity of kinetic viscosity in the commercially available product of each silicone composition
Rate) (such as, 1~100000mm2/ s) set.
(changing 2)
But, R3: methyl, m, n: identical or different arbitrary integer.
(changing 3)
But, R4: methyl, R5: phenyl, m, n: identical or different arbitrary integer.
(changing 4)
But, R6: methyl, n: integer.
(changing 5)
But, R7: methyl, RX: functional group's substituted hydrocarbon radical, m, n: identical or different arbitrary integer.
Here, as functional group's substituted hydrocarbon radical, can enumerate be instead of by amino, epoxy radicals, hydroxyl, sulfydryl, carboxyl etc.
Alkyl, phenyl etc..
(changing 6)
But, R8: methyl, RX: functional group's substituted hydrocarbon radical, n: arbitrary integer.
As above-mentioned functional group substituted hydrocarbon radical, can enumerate identical with above-mentioned formula (5).
(changing 7)
But, R: alkyl, R8: methyl, RX: functional group's substituted hydrocarbon radical, n: arbitrary integer.
As above-mentioned functional group substituted hydrocarbon radical, can enumerate identical with above-mentioned formula (5).
(changing 8)
But, R9: methyl, RX: functional group's substituted hydrocarbon radical, m, n: identical or different arbitrary integer.
As above-mentioned functional group substituted hydrocarbon radical, can enumerate identical with above-mentioned formula (5).
(changing 9)
But, R10、R11: 1 valency alkyl, the integer of m:0~2, the integer (R of n:0~400 (preferably 5~250)10、R11Phase
Same or different).
It addition, as the commercially available product of reactive silicone oil, " X-22-173BX ", " X-22-170BX ", " X22-can be enumerated
174ASX " (being SHIN-ETSU HANTOTAI's chemical industry (strain) trade name processed above) etc..
These reactive silicone oil can be used alone, it addition, also can two or more be used together.
The commercially available product of silicone oil as latex, can enumerate as methyl Hydrogen " TSW831 " that (hardening accelerator adds
Add product) (MOMENTIVE high performance material Japan co-partnership company trade name), as amino modified type " KP2601 ",
" NP2609 " (rising sun WACKER silicone (strain) trade name processed) etc..
It addition, as non-reacted silicone oil, solid-state/emboliform can be used.As commercially available product, can enumerate microgranular
" X52-1621 " (SHIN-ETSU HANTOTAI's silicone (strain) trade name processed) etc..It should be pointed out that, that non-reacted silicone oil also becomes with other silicone
As Fen, play the effect that the hydrophobicity of firming body gives, but in the case of as curing materials composition, with other solidification material
The intermiscibility of material composition is poor, the most preferably not as gradation composition.
It is preferably less than 5 parts relative to the use level of the silicone oil of silicone oligomers 100 parts, more preferably less than 3 parts.Silicon
The use level of ketone oil is the biggest, and for firming body, the acquisition of practical intensity is just more difficult to, and the maintenance difficulty of latex form strengthens.
(III) fluorine-containing organoalkoxysilane:
It is preferably the alkoxysilane represented by following formula (10).They can mix alone or in any combination makes
With.It should be pointed out that, in formula (10), by " CF2" conduct "-O-CF2" with season " x=1~10 " perfluoroalkyl polyether
(fluoropolyether) the fluorine-containing organoalkoxysilane of type also may be used.
(changing 10)
But, R12: the alkyl of C1~C4 or alkoxyl, R13、R14: alkoxyl (identical or different), the integer of x:0~10,
The integer of Y:0~2.
As above-mentioned R12Represented alkyl, can enumerate such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, secondary
Butyl, the tert-butyl group etc..
It addition, R12、R13、R14Represented alkoxyl, can enumerate such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy,
The alkoxyl of C1~C4 such as butoxy, isobutoxy, sec-butoxy, tert-butoxy.Wherein, preferably R12、R13And R14All
Methoxyl group.These alkoxysilane can be used alone, additionally, it is possible to two or more is used together.
As concrete chemical combination name, perfluoro hexyl ethyl trimethoxy silane (perfluorohexyl can be enumerated
Ethyl trimethoxysilane), perfluorooctylethyl group trimethoxy silane (perfluorooctyl ethyl
Trimethoxysilane), perfluor heptyl ethyl trimethoxy silane (perfluoroheptyl ethyl
Trimethoxysilane), perfluoro butyl ethyl trimethoxy silane (perfluorobutyl ethyl
Trimethoxysilane), perfluoro propyl ethyl trimethoxy silane (perfluoropropyl ethyl
Trimethoxysilane), perfluoro-ethyl ethyl trimethoxy silane (perfluoroethyl ethyl
Trimethoxysilane) etc..
It is preferably less than 10 parts, more preferably relative to the use level of the alkoxysilane of silicone oligomers 100 parts
It it is less than 5 parts.If the use level of fluoroalkoxy silane based compound is more than 10 parts, then may cause the hydrosol state can not
Maintain.
(IV) alkoxy silane:
Monoalkoxysilane, dialkoxy silicane, trialkoxy silane or four represented by following formula (11) can be enumerated
Alkoxy silane.Wherein, preferred trialkoxy silane.
(changing 11)
But, RA: alkoxyl, RB、RC、RD: alkyl or alkoxyl (identical or different).
As preferred alkoxysilane compound containing trialkylsilyl group in molecular structure, heptyl trimethoxy silane, hexyl trimethoxy silane, fourth can be enumerated
Base trimethoxy silane, propyl trimethoxy silicane etc..
These alkoxy silane based compounds can be independent, also can two or more be used together.
It should be pointed out that, in silicon-ketone composition that other the silicone composition relative to silicone oligomers 100 parts (silicone oil, contains
Fluorine organoalkoxysilane, alkoxy silane) use level be preferably less than 5 parts, more preferably less than 3 parts.If other
The use level of silicone composition too many, then crumbling property (resistance to mud again) during the intensity of firming body may be caused low, water-fast
Lowly.
(V) surfactant:
The silicon-ketone composition of the present application generally all comprises containing each composition, in order to mix with latex form, makes
With when being not added with the silicone composition of surfactant, surfactant to be added.
As surfactant, as long as silicone can be stably maintained at latex (hydrosol), then indefinite.Can use
Following cation system, anion system.
Cation system: alkylamine salt, quaternary ammonium salt, ethyleneoxide addition type quaternary ammonium chloride etc..
Anion system: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, dehydration mountain
Pears alcohol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine etc..Wherein, preferred polyoxyethylene alkane
Base ether, polyoxyethylene fatty acid ester, fatty acid esters of sorbitan, polyoxyethylene sorbitan fatty acid ester.
These surfactants can one be used alone, it is possible to is used in combination.
More specifically, " the LIONOL as oxygen vinyl alkyl ether (polyoxyethylene alkyl ether) can be enumerated
TDL20/TDL30 ", as polyoxyethylene alkylamide " Esomaido HT16 ", " Esomaido O15 " (amide) (more than
For LION (strain) trade name processed).
< (3) hardens adjuvant >
In the curing materials of the present invention, in order to make firming body obtain practical intensity and hardening adjuvant to be added.
Hardening adjuvant preferably comprises hardening accelerator (I), bacillus generates Hydraulic binding between accelerator (II) and particle and subtracts
At least one in low dose (III).Each composition is suitably selected according to the kind of treated object.
Really can possess hydrophobicity possess again simultaneously water-fast in crumbling property and then harmful heavy metal class can be suppressed to elute
Such, require high intensity, unwetted (watertightness) in the case of, it is raw that curing materials preferably comprises hardening accelerator, bacillus
Hydraulic binding between accelerator and particle is become to lower the whole composition of agent.
During it addition, treated object is floatability ultrafine powder, more preferably coordinate agglutinant.
It should be pointed out that, for hardening adjuvant in harm the associativity to cement or even the silicon-ketone composition of ultrafine powder with
And the hydrophobic composition of firming body, reduce its addition as far as possible.
It addition, in the following description, illustrate as the compound being best suitable for each hardening adjuvant, be not limited only to
To the effect of each sclerosing agent auxiliary element, there is also the situation simultaneously working as other effects.
Such as, play bacillus and generate the FeCl of accelerator effect3May also function as the effect of the agglutinant of ultrafine powder.Play particle
Between Hydraulic binding lower agent effect NaCl, K2CO3May also function as the effect that bacillus generates the adjuvant of accelerator.It addition, weak base
The Na of property2CO3、K2CO3, weakly acidic MgCl2、CaCl2PH regulator can be also served as.
(I) hardening accelerator
Adding ultrafine powder to and contain thing when making it solidify, the intensity in order to ensure obtained firming body is necessary.
In the case of it should be pointed out that, slag cements, owing to containing the hardening adjuvant (MgCl of the present application in advance2、MgSO4Deng), institute
With the necessity do not added on coordinating.
As hardening accelerator, specifically, CaCl can be suitably used2、MgCl2(particularly CaCl2) etc., but also can make
Use CrO4 2-、S2O4 2Ca salt, and then it be also possible to use expanding coefficient and the high chloride (Cl of water solubility-Ionic compound) (please
See Japanization association volume " the 5th edition chemical brief guide applied chemistry piece I " (flat 7-3-15) ball to be apt to, page 394, table 5.58).
These hardening accelerators compounding ratio in hardening adjuvant is different according to the kind of hardening accelerator, not
It is particularly limited to.Such as, the scope at 10-80% is the most selected.
(II) bacillus generates accelerator
(cement) bacillus (bacillus) refers to entringite (3CaO Al2O3·3CaSO4·32H2O) (Ca system needle-like knot
Brilliant), be by make firming body generates the Ca system acicular crystal of resistance to water, with the pore of this acicular crystal filling firming body,
Thus suppress firming body water to crumble (mud again), suppress heavy metal etc. from solidification
This bacillus generates accelerator can use iron family element chloride FeCl3Deng, but preferably CoCl2.With metal chloride
(MgCl2、NaCl、FeCl3), basic carbonate is as accessory ingredient.
It is relevant with other hardening adjuvant that bacillus generates accelerator ratio in firming body, and is not particularly limited.Hardening
CoCl in adjuvant2Compounding ratio be preferably 3~12%.
(III) between particle, Hydraulic binding lowers agent
Lower agent as this Hydraulic binding, be used as in cement admixture in the hydroxy carboxylic acid of condensation delayed-action activator, preferably lemon
Lemon acid.Hydroxy carboxylic acid beyond citric acid, such as, gluconic acid, tartaric acid, malic acid etc. there is also the probability of use.
Hydroxy carboxylic acid is bonded with hydroxyl by the carboxyl of cement surface and makes cement hydration postpone, and stops owing to hardening rapidly
And the compactness caused is lowly, so that it is guaranteed that firming body intensity.In the present application, make hydration knot between the micropartical of treated object
Close and lower, thus play hinder cement Ca composition hydration (in conjunction with) effect reacted.
Existing those skilled in the art conventional wisdom is that, (between particle, Hydraulic binding is strong i.e. to use cement to make laterite.), organic
Mountain soil, field soil that (humus) content is high harden, and firming body can not be made to obtain enough practical intensity.I other words, if cement
In containing organic substance (particularly saccharide), then hydration reaction postpones, if the amount of saccharide increases, the most quickly can become non-condensing.
As long as being thought that and using the existing citric acid being used as to condense in the hydroxy carboxylic acid of delayed-action activator just can obtain above-mentioned red
Soil, the firming body of field soil.At that time, it was additionally considered that best and relatively large number of strong electrolyte was used together.
Its reason is considered as, " by improving containing K+、Na+Or Mg2+The concentration of strong electrolyte, hydrability also increases, super
Powder body interparticle hygroscopic water gravitation reduces thus the solution of agglutination body solidifying (deflocculate) advances.Therefore, Ca2+(cement
) intrusion laterite, between ultrafine powder particle, thus cement becomes bonding agent and works.”
It should be pointed out that, Na+、K+(1 race, 2,3 cycles) ion footpath is little, Mg2+、Ca2+(2 races, 2,3 cycles), ion footpath was relatively
Little and ioni valence is high thus hydration easily (refers to " inorganic chemistry " wide river publish, page 139 " property of § 9.9 strong dielectric solution
Matter ").
As concrete strong electrolyte, NaCl, KCl, MgCl can be enumerated2、CaCl2、Na2CO3、K2CO3、Na2SO4、K2SO4
Deng.
In hardening adjuvant, Hydraulic binding lowers the compounding ratio of agent and is preferably in the case of citric acid 2~5% between particle.
Other secondary agent > of < (4)
Add silicon-ketone composition (hydrophobicity-imparting agent) to above-mentioned cement, add hardening adjuvant, can properly select
The existing known material as cement admixture is used, and the secondary agent as other (refers to Japanization association and compiles " change
Learn a brief guide application piece and change fixed 3 editions " (clear 55-3-15) ball is kind, and page 394, table 5.58).Intermixture refers to contribute to manufacturing with cement
The material that improves of the physical property of the firming body such as concrete.
I other words, suitably can coordinate agglutinant, pH regulator, high-moisture absorbing material, thickening agent in curing materials
(PVAL), the existing intermixture being used in cement such as antifoaming agents/dispersant, pigment etc..It should be pointed out that, as agglutinant, it is possible to
Use polymer coagulant, but preferably FeCl3Deng inorganic agglutinant, it is susceptible to the impacts such as lonizing radiation.
It addition, in the case of manufacturing the concrete curing body that reinforcing bar is distributed, for reinforcing bar corrosion protection (antirust), preferably make
It contains and has the nitrite of metal ion removal effect, rhodanate (rhodanate), phosphoric acid.
Other the use level of secondary agent above-mentioned does not limit, as long as in the scope of the intensity not harming firming body.
It addition, in the curing materials of the present application, when firming body manufactures, coordinate paper fiber, plastic optical fibre, glass fibers
The supporting materials such as dimension, carbon fiber, metallic fiber, then coordinate the aggregates such as gravel, enhancing firming body intensity/generation be full of cracks can be obtained and send out
The effects such as life, make firming body utilizes expanded range.
B. the manufacture method of the firming body of the curing materials using the present application is illustrated.
(1) in the mud (treated object) of the scheduled volume put in the mixing containers such as blender, with described curing materials
Silicon-ketone composition simultaneously suitably add water, as homodisperse slurry (mud).
(2) in this slurry, the cement (inorganic bonding agent) of mixing cured material is added and as homodisperse mixing
Thing.This mixing thing is cast in the mould of arbitrary dimension, aoxidizes under room temperature or low-temperature heat pressurized conditions, manufacture block
Shape or the granular or firming body of mould block-wise.
Silicon-ketone composition, the ordering in launching of cement above-mentioned do not limit, if but before silicon-ketone composition puts into input cement,
The dissolution dispersity that then may cause cement is low.
Firming body manufactured above, possess intensity and hydrophobic while, also have water-fast in crumbling property and having
Evil heavy metal class elution inhibition.I other words, the hardening thing of the silicon-ketone composition of the present invention, for light, heat, lonizing radiation etc. relatively
Being stable, therefore, imparting firming body is to use the excellent hydrophobicity under environment or even unwetted on a large scale, and then also gives
Crumbling property (non-mud again) and long-time intensity maintenance during it is water-fast.
Therefore, when the mud containing polluter in a large number is isolated for a long time preservation as firming body, storage-stable is good.
Particularly, if being applied to contain in a large number the mud of the harmful substances such as asbestos, radioactive substance, heavy metal, then have better effect.
It addition, with the present invention manufacture firming body, keep intact or suitably pulverize after, can be used for soil modifier,
Reclamation, and then can be additionally used in fish shelter etc..
Can be as the regeneration firming body of higher intensity additionally, above manufactured firming body is as described below.
Firming body is suitably carried out pulverization process so that it is become the thing broken processed that particle diameter is adjusted in preset range.To this
Broken thing processed adds the curing materials of described the present application of scheduled volume and water and becomes mixing thing.Now, as required,
In this curing materials, use the various aggregate/supporting materials beyond described firming body simultaneously, described mixing thing modulated,
It is cast in predetermined mould, under room temperature or low-temperature heat pressurized conditions, carries out maintenance hardening, and then height can be manufactured
The regeneration firming body coming from mud of intensity.
Therefore, the manufacture method of the regeneration firming body of the present invention can expand the application of Reinforced Concrete Materials, Jin Erkuo
The application in civil construction field such as syphon, cement pre-fabricated panel, roadbed material.
Embodiment
Hereinafter, enumerate the experimental example containing embodiment and the present invention is illustrated, but the present application is not by following experiment
Example is limited.
< curing materials component materials >
Each component materials that test example is used is as follows.
(A) cement (bonding agent)
A1: commercially available portland cement
Composition ... SiO2: 21.1%, Al2O3: 5.3%, Fe2O3: 2.4%, CaO:66.2%, MgO:1.6%, SO3:
2.3%, Na2O:0.3%, K2O:0.4%, TiO2: 0.1%
A2: portland blast-furnace slag cement
Composition ... MgO:3.31%, SO3: 2.05%, Cl-: 0.01%
(B) humidity-hardening silicone oligomers
B1: " KR-400 " (SHIN-ETSU HANTOTAI's chemical industry (strain) trade name processed), viscosity 1.2mPa.s/25 DEG C, proportion 0.98/25
℃
B2: " SILRES BS SMK 2101J " (Asahi Chemical Industry's WACKER silicone (strain) trade name processed), viscosity 1~
10mPa.s/25 DEG C, proportion 0.9/25 DEG C
B3: " SILRES BS POWDER A " (Asahi Chemical Industry's WACKER silicone (strain) trade name processed), octyl group triethoxy
Silane Silicon stone type (octyltriethoxysilane silica type), bulk specific gravity 500kg/m2
(C) (reactive) silicone oil
C1: " X-24-9377 " (SHIN-ETSU HANTOTAI's chemical industry (strain) trade name processed), methoxy-type, 6mPa.s/25 DEG C
C2: " X52-1621 " (SHIN-ETSU HANTOTAI's silicone (strain) system), spherical silicone oil, mean diameter 5 μm, true specific gravity 0.99
(D) fluorine containing silane (fluoro alkyl-silane)
D: perfluoro hexyl ethyl trimethoxy silane (perfluorohexyl ethyl trimethoxysilane)
(E) alkoxy silane:
E: hexyl trimethoxy silane (hexyl trimethoxysilane)
(F) surfactant
F: nonionic surfactant (polyoxyethylene alkyl ether)
(G) hardening adjuvant
GM:KCl, NaCl, CaCl2、MgCl2、FeCl3、K2CO3, citric acid, Na2SO4(adding up to 100 parts)
(T) aggregate:
It is dried river sand
(R) supporting material:
Glass fibre (average fiber length: 13mm, filament diameter: 10 μm)
(H) mud etc. (treated object)
Coal ash (moisture 27.0%)
Laterite (moisture 27.0%)
(S) reflective substance:
" IOMIX POWDER " Mino Ganryo Kagaku Corporation's trade name, 1kg/ dose equivalent (2.650 μ Sv/h,
Measure distance: 10mm, survey fixed time humidity: 60%)
The modulation > of < silicone (compositions)
In silicone oligomers, add silicone oil, fluoro alkyl-silane, alkoxy silane or table shown in table 1 as shown formula
Face activating agent, mixes with homogenizer, thus is modulated each silicon-ketone composition 500g.Married operation sets returning of homogenizer
Revolution 5000rpm, mixes three minutes.These silicon-ketone compositions easily latex.
(table 1)
(unit: mass parts)
The modulation > of < hardening adjuvant
With eddy current (whirling) type blender (" DB2264 " Bei Yin (strain) trade name processed), the formula as described in table 2
The each composition (compound) making the hardening adjuvant described in this table mixes equably/disperses, thus to hardening adjuvant (GM)
Modulated.
(table 2)
(unit: matter %)
Chemical combination name | GM forms |
Calcium chloride (CaCl2) | 15.0 |
Potassium chloride (KCl) | 21.0 |
Sodium chloride (NaCl) | 20.0 |
Cobaltous chloride (CoCl2) | 6.0 |
Magnesium chloride (MgCl2) | 20.0 |
Iron chloride (FeCl3) | 2.0 |
Potassium carbonate (K2CO3) | 10.0 |
Citric acid | 3.0 |
Calcium sulfate (Na2SO4) | 3.0 |
Add up to | 100.0 |
The preparation > of the experiment body of < comparative example/embodiment
In coal ash or laterite, by formula shown in table 3 or table 4 (1)~(4), add the silicone combination of curing materials
Thing and hardening adjuvant (only adding hardening adjuvant in comparative example), then add the cement of curing materials with water simultaneously, thus
Mixing thing is modulated.This mixing thing is cast toMould in, at room temperature place after 3 days de-
Mould, carries out air-drying maintenance 25 days afterwards in indoor, thus prepared comparative example 1~4 and embodiment 1~34 respectively test body.
(table 3)
(unit: mass parts)
(table 4 (1))
(table 4 (2))
(table 4 (3))
(table 4 (4))
(unit: mass parts)
The preparation > of the experiment body of < Application Example
With sieve, the broken thing of the experiment body (firming body) prepared by embodiment 1,2,23,24 is adjusted to 0.5~5.0mm
After particle diameter, the formula as shown in table 5 adds the silicon-ketone composition as curing materials, hardening adjuvant, then adds with water simultaneously
Add cement (water/cement ratio 0.55), thus mixing thing is modulated.This mixing thing is cast toMould
In tool, at room temperature place the demoulding after 3 days, carry out air-drying maintenance 28 days afterwards in indoor, thus prepared Application Example 1~
4 respectively test body.
(table 5)
(unit: mass parts)
< evaluation of physical property experimental technique >
To for confirm the effect of the present application and to comparative example, embodiment and each experiment prepared by Application Example
The experimental technique that body is carried out is illustrated.
(1) hydrophobicity evaluation experimental
Hydrophobic mensuration after experiment body is at room temperature carried out air-dried maintenance in 28 days, put it into holding 10 DEG C
Air drying agent machine is dried after 6 hours take out, keeping more than 18 hours laggard in exsiccator (Desiccator) again
Row.
Being immersed by the above-mentioned experiment body taken out from exsiccator in the water of 20 DEG C after 20 minutes, from water, withdrawal, passes through mesh
Survey and its surface state of soaking is observed.
Hydrophobic metewand by range estimation is as follows.
◎: play water, do not stay and soak vestige.
Zero: although playing water, but leave some and penetrate into vestige.
△: although there being a little part playing water, but verified infiltration vestige accounts for more than the 50% of entirety.
×: entirely without the sign playing water
(2) water absorption rate determination experiment
If the water absorption of firming body is high, then the area of this firming body contact water increases, and there is the trend promoting again argillization.Separately
Outward, the hydrophobicity of sludge curing body and the inversely proportional relation of water absorption.Therefore, water absorption rate is measured in the steps below.In room temperature
Under carry out air-drying maintenance 14 days to experiment body after, be determined according to " JIS A52085.2 ".
(3) compressive strength determination experiment
If the intensity of sewage sludge solid is big, then there is the effect making its purposes expand, thus measure pressure in the steps below
Contracting intensity.
After at room temperature carrying out each experiment body air-drying maintenance 14 days, it is determined according to JIS A-1108.
< evaluation experimental result >
(1) during the experimental result of each comparative example/embodiment is shown in table 3, table 4 (1)~(4).
From the experimental results, the experiment body of each embodiment of the present application is in addition to embodiment 13,14, and any one all has
There is excellent compressive strength, there is excellent hydrophobicity simultaneously, and water absorption rate is relatively low, it is possible to confirm to serve the present application
Effect.
Although it should be pointed out that, the embodiment 13,14 that silicon-ketone composition does not coordinates with reactive silicone oil or fluoro alkyl-silane
Compressive strength is higher, but compared with other embodiments, hydrophobicity or even unwetted are less better.
On the contrary, on the other hand, the reality of the most unmated silicon-ketone composition comparative example 1,3 of the most unmated hardening adjuvant simultaneously
Testing body, even compared with embodiment 13,14, compressive strength is the lowest, and hydrophobicity or even unwetted are the most very poor simultaneously.
(2) experimental result of Application Example is shown in Figure 5.
Can learn from experimental result, the regeneration firming body made with the firming body ground product of the present application, with each enforcement
Example is compared, and while compressive strength is splendid, hydrophobicity or even unwetted are the most splendid.
Other evaluating characteristics experiment/experimental result > of <
If the heavy metal class elution contained in firming body, pollute the environment.Therefore, in the steps below to from firming body
The elution amount of the heavy metal of elution is determined.
For the experiment body of embodiment 5, by the analysis method being shown in table 6, the elution amount of each metallic element is carried out quantitatively
Analyze.Significantly inhibit, it can be confirmed that the firming body of the present invention has, the effect that heavy metal class elutes from the table 6 illustrating analysis result.
It should be pointed out that, that the amount of metal analytical table of the coal ash that embodiment 5 used is shown in Table 7 as reference.
(table 6)
(unit: mg/L)
Project | Assay value | Lower limit of quantitation value | Soil environment reference value | Analysis method |
Cadmium | <0.001 | 0.001 | ≤0.01 | JIS K 0102-56.2 |
Lead | < 0.005 | 0.005 | ≤0.01 | JIS K 0102-54.2 |
Cr VI | <0.01 | 0.01 | ≤0.05 | JIS K 0102-65.2 |
Arsenic | < 0.005 | 0.005 | ≤0.01 | JIS K 0102-61.2 |
Total mercury | <0.0005 | 0.0005 | ≤0.0005 | Environmental Agency's bulletin the 69th |
Selenium | <0.001 | 0.001 | ≤0.01 | JIS K 0102-67.2 |
(table 7)
(unit: mg/L)
Project | Content | Project | Content |
Total mercury | 0.05 | Be | 3.2 |
Cd | 0.25 | Co | 35.00 |
Pb | 91.00 | Cu | 85.00 |
Cr6+ | 55.00 | Mn | 590.00 |
As | 42.00 | N | 26.00 |
Cl | 77.00 | Ni | 22.00 |
F | 160.00 | Li | 17.00 |
Se | 0.97 | Sr | 790.00 |
B | 160.00 | Zn | 45.00 |
Ba | 1800.00 |
(2) the confirmation experiment deteriorated due to radiant
In order to investigate lonizing radiation that the radioactive substance contained from sludge curing body radiated to sludge curing body institute shape
The hydrophobic performance become is the lowest, feed through to the impact of the lonizing radiation of hydrophobic phenomenon, is tested in the steps below.
Radioactive substance 3.0 parts is added, as previously mentioned to portland cement 96.40 parts, silicon-ketone composition (B2) 0.60 part
Similarly prepare experiment body.
This experiment body is fixedly installed on outdoor on October 27th, 24 to Heisei on March 21st, 21 from Heisei, is exposed to wind
Rain, is routinely observed hydrophobic phenomenon during rainfall.As a result, interior hydrophobicity (◎), water absorption rate
(1.20%) unchanged, last and within about 3 years half, there is no notable change.
(3) example (impact adding hardening adjuvant to firming body confirms experiment) is seen
Remove add in cement hardening adjuvant constituent (metal chloride, citric acid, cobaltous chloride, carbonic acid/
Alkali sulfate) the composition of hardening adjuvant GM1~GM9 of a part be shown in Table 8.
And, in using the formula of comparative example 2 (table 3) of each hardening adjuvant, by auxiliary for hardening adjuvant GM hardening
Auxiliary agent GM1~GM9 instead outside, in the same manner as comparative example 2 to see example experiment body modulated, similarly carried out hydrophobic
Evaluation, water absorption rate and the experiment of compressive strength.
These results are shown in Table 8.From this result it can be seen that with hardening accelerator (CaCl2、KCl、MgCl2) bar together
Bacterium generates agent (CoCl2) be to ensure that necessary to intensity.
Citric acid cuts off the gravitation produced between ultrafine powder particle and makes the calcium component of cement solution be impregnated with expansion between particle
Dissipate thus contribute to the intensity increase of firming body.But, the coal ash that experimental example is used does not contains organic composition (humic acids
(humic acid)), thus the contribution increasing intensity is less.But.The water absorption rate of the GM8 without citric acid is the highest, from this
Can be seen that citric acid has unwetted increase effect (firming body densification).
Additionally, it is believed that CaCl2Metal chloride in addition secondarily promotes that the hardening (solidification) of cement is reacted, CoCl2With
Na2SO4, cement calcium component formed acicular crystal thing, play enhancing resistance to water, the effect of watertightness.
(table 8)
(4) experimental example I (the use probability of air-hardening cement confirms experiment) is added
For air-hardening cement, from the understanding of the present inventor adding citric acid anhydrous gypsum and make laterite solidify
See, in slaked lime (mortar), add the hardening adjuvant GM that other compositions all contain together with citric acid, make field native and red
Soil solidifies and is made for firming body.This firming body is sunk to marine, carried out water-fast in the experiment of crumbling property.In this experiment,
Though achieving substantially achievement, if but anhydrous gypsum contains foreign body, leads due to the condition (temperature and moisture) during hardening the most sometimes
Cause the generation of bacillus excess thus be difficult to obtain the intensity of practicality.Therefore, need in the case of being used together with hardening adjuvant
Adjust coordinate, but can by silicon-ketone composition to air-hardening cement hydrophobic property the fact that confirmed.
And, the additional experimental example prepared coordinating silicon-ketone composition B3 to make it harden in anhydrous gypsum or slaked lime
The firming body of I-1 and I-2 and with laterite, anhydrous gypsum and only the hardening adjuvant of citric acid combination or with field soil,
The combination of slaked lime and hardening adjuvant GM is mixing, make it harden in atmosphere and the consolidating of additional experimental example I-3~I-5 that prepare
Change body, carry out above-mentioned evaluation experimental.
From illustrating the table 9 of evaluation experimental result it can be seen that the silicon-ketone composition of the present application fully imparts hydrophobic
Property, even if it addition, from additional experimental example I-3 it can be seen that the composition of hardening adjuvant is individually for citric acid, also playing enough
Intensity increase effect.
(table 9)
(unit: mass parts)
(5) experimental example II (solidification of the hardening adjuvant of Organic Sludge confirms experiment) is added
The most generally acknowledged cement makes a large amount of hardening containing organic field soil or mountain soil be difficult to.Therefore, to having coordinated bagasse (Caulis Sacchari sinensis
Slag) field soil, use cement A1, and make it harden with the hardening adjuvant GM of the present application and prepared additional experimental example
The firming body of II-1~II-3, and these firming bodys have been carried out above-mentioned evaluation experimental.It should be pointed out that, required for complexing compositions
The water yield adjusted to make slump value (slump value) be 20~22cm.
The result of evaluation experimental is shown in Table 10.The hardening adjuvant containing citric acid of the present application can obtain practicality
Confirmed the fact that of intensity.
(table 10)
(unit: mass parts)
Claims (11)
1. a curing materials, this curing materials is mixed into ultrafine powder for interpolation and contains and make it solidify in thing, and by with nothing
The host that machine binding agent is constituted and the secondary agent containing hydrophobicity-imparting agent and hardening adjuvant are constituted, wherein, described hydrophobic
Property imparting agent is to be made up of moisture-curable type silicone oligomers or based on the silicon-ketone composition of this silicone oligomers.
2. curing materials as claimed in claim 1, wherein, described silicon-ketone composition is possibly together with silicone oil, fluorine-containing organic group alkane
At least one in TMOS and alkoxy silane.
3. curing materials as claimed in claim 2, wherein, described silicone oil is reactive silicone oil, described fluorine-containing organic group
Alkoxy silane is alkoxysilane.
4. the curing materials as described in claim 1,2 or 3, wherein, described silicone oligomers is alcoxyl shown in general formula (1)
The partial hydrolysis condensate of base silane:
R1 X Si(OR2)4-X (1)
But, R1Represent hydrogen atom or 1 substituted or non-substituted valency alkyl, R2Representing alkyl, x is the integer of 0~3.
5. the curing materials as according to any one of Claims 1 to 4, wherein, described hardening adjuvant is hardening accelerator, bar
Bacterium generates at least one between accelerator and particle in Hydraulic binding attenuating agent.
6. curing materials as claimed in claim 5, wherein, described hardening accelerator contains CaCl2, described bacillus generates and promotes
Agent contains CoCl2, and between described particle, Hydraulic binding attenuating agent contains citric acid.
7. curing materials as claimed in claim 6, wherein, described hardening accelerator is possibly together with alkaline metal salt, and described grain
Between son, Hydraulic binding lowers agent possibly together with basic carbonate.
8. the curing materials as according to any one of claim 1~7, wherein, described secondary agent is possibly together with inorganic agglutinant.
9. the curing materials as according to any one of claim 1~8, wherein, described inorganic bond is cement.
10. ultrafine powder contains a curing for thing, and this curing uses the solidification any one of claim 1~9
Material solidifies described ultrafine powder and contains thing, and wherein, this curing includes following procedures:
(1) contain in thing to described ultrafine powder, the most suitably add water with the silicon-ketone composition of described curing materials and make
Operation for homodisperse slurry;And
(2) add in this slurry and mix the cement of described curing materials as homodisperse mixing thing, and at room temperature or low
Make this mixing thing maintenance hardening under temperature heating pressurized conditions and as the operation of firming body.
11. 1 kinds of manufacture methods regenerating firming body, wherein, under room temperature or low-temperature heat pressurized conditions, make mixing thing maintenance
Hardening is as regeneration firming body, and described mixing thing is through to the broken system of the firming body obtained by the method described in claim 10
Thing adds curing materials any one of claim 1~9 again and water modulated.
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CN110419411A (en) * | 2019-09-04 | 2019-11-08 | 陕西科技大学 | A kind of Nutrition Soil and its method of administration repaired for mine with revegetation |
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JP2004210588A (en) * | 2002-12-27 | 2004-07-29 | Takasu Ai System:Kk | Solidification assisting composition and its producing method |
CN102712811A (en) * | 2010-01-18 | 2012-10-03 | 日本实行株式会社 | Silicone resin composition and protective coating method using silicone resin composition |
CN103038188A (en) * | 2010-04-01 | 2013-04-10 | 赢创德固赛有限公司 | Curable mixture |
JP2013107966A (en) * | 2011-11-18 | 2013-06-06 | Green Arrows Central Co Ltd | Soil solidifying material |
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JPH03261642A (en) * | 1990-03-09 | 1991-11-21 | Toray Dow Corning Silicone Co Ltd | Hydraulic inorganic composition |
JP2004210588A (en) * | 2002-12-27 | 2004-07-29 | Takasu Ai System:Kk | Solidification assisting composition and its producing method |
CN102712811A (en) * | 2010-01-18 | 2012-10-03 | 日本实行株式会社 | Silicone resin composition and protective coating method using silicone resin composition |
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