CN100345792C - Spraying material and spray technique employing the same - Google Patents
Spraying material and spray technique employing the same Download PDFInfo
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- CN100345792C CN100345792C CNB200480001078XA CN200480001078A CN100345792C CN 100345792 C CN100345792 C CN 100345792C CN B200480001078X A CNB200480001078X A CN B200480001078XA CN 200480001078 A CN200480001078 A CN 200480001078A CN 100345792 C CN100345792 C CN 100345792C
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Abstract
Provided is a spraying material having an excellent quick-setting property and excellent adherability, a small alkali amount and excellent initial strength development, and a spraying method using it. The spraying material comprises a liquid quick-setting admixture containing an aluminum source, a sulfur source and a fluorine source, one or more quick-setting aids selected from the group consisting of calcium aluminate, calcium sulfoaluminate, calcium aluminosilicate, an alkali metal-containing substance, calcium hydroxide and aluminum hydroxide, and a cement concrete, and the method is to spray this spraying material.
Description
Technical field
The present invention relates in tunnel of domatic or road, railway or catchwater etc. etc., spray to the spraying coating process that exposes the spray material on the massif face and adopt this material.
Background technology
In the past, in the digging operation in tunnel etc., for the landslide that prevents to expose, use the method (with reference to the public table of Japan's special permission communique clear 60-004149 number, open the flat 09-019910 of communique number of Japan's special permission) of the rapid hardening concrete spraying that mixed powder accelerating chemicals in the concrete is formed.
As the used accelerating chemicals of these spraying coating process, available alkali aluminate metal or carbonic acid an alkali metal salt etc. are blended in the material that forms in the calcium aluminate, because this material has excellent rapid hardening performance.
But,,, preferably need neutrality or weakly acidic accelerating chemicals so people need weakly alkaline owing to be that pH value is lower than the pH value that alkali aluminate metal-salt or carbonic acid an alkali metal salt are blended in the accelerating chemicals that forms in the calcium aluminate.
As so liquid accelerating chemicals, proposition is the accelerating chemicals (showing communique 2001-509124 number with reference to the Japanese public affairs of speciallyying permit) of main component, is the accelerating chemicals of principal constituent (speciallyying permit openly the flat 10-087358 of communique number with reference to Japanese) with Tai-Ace S 150 or alkanolamine with basic aluminium salt and organic carboxyl acid; And with alkaline aqueous solution, lithium silicate and the lithium aluminate of aluminium the accelerating chemicals etc. of principal constituent (with reference to open communique 2001-130935 number of Japan's special permission).
But these liquid accelerating chemicalss are difficult to manifest initial strength, compare with powder class accelerating chemicals in the past, exist to be difficult to make the stiff problem of spraying in the hole, tunnel.
As the acid liquid accelerating chemicals that has improved rapid hardening, also developed the accelerating chemicals (with reference to open communique 2002-080250 number of Japan's special permission, open communique 2002-047048 number of Japan's special permission, open communique 2004-035387 number of Japan's special permission) that contains fluorine at Tai-Ace S 150.
But when practicality, the adhesivity at water position etc. is overflowed in further raising rapid hardening of requirement, raising.In addition, in recent years, expectation can be developed influence to human body and is less than in the past liquid accelerating chemicals alkaline accelerating chemicals, manifesting property of initial strength excellence.
Summary of the invention
In view of above situation, the present inventor has carried out the various discussions that address the above problem, and the result has obtained following discovery: use when having the spray material of specific composition, can make that alkali number is few, the good spray material of manifesting property of initial strength, and finished the present invention.
Therefore, the present invention is made of following main points:
1. spray material is characterized in that, contains liquid accelerating chemicals, rapid hardening auxiliary agent and cement concrete and forms; Liquid accelerating chemicals contains aluminium source, sulphur source and fluorine source; The rapid hardening auxiliary agent is selected from a kind of in material, calcium hydroxide and the aluminium hydroxide of calcium aluminate, calcium sulphoaluminate, ca aluminosilicate, alkali metal containing or more than two kinds.
2. according to above-mentioned 1 described spray material, it is characterized in that, with respect to being converted into SO
3100 parts in sulphur source, with Al
2O
3Convert, the aluminium source of liquid accelerating chemicals is 25-110 part.
3. according to above-mentioned 1 or 2 described spray material, it is characterized in that, with respect to being converted into SO
3100 parts in sulphur source, the fluorine source of liquid accelerating chemicals is 2-50 part as F.
4. according to each described spray material among the above-mentioned 1-3, it is characterized in that liquid accelerating chemicals also contains alkanolamine.
5. according to above-mentioned 4 described spray material, it is characterized in that, with respect to being converted into SO
3100 parts in sulphur source, alkanolamine is 1-30 part.
6. according to each described spray material among the above-mentioned 1-5, it is characterized in that liquid accelerating chemicals also contains alkali metal source.
7. according to above-mentioned 6 described spray material, it is characterized in that, with respect to being converted into SO
3100 parts in sulphur source, with R
2O converts (R is a basic metal), and alkali metal source is 2-50 part.
8. according to each described spray material among the above-mentioned 1-7, it is characterized in that the pH of liquid accelerating chemicals is below 6.
9. according to each described spray material among the above-mentioned 1-8, it is characterized in that, the usage quantity of liquid accelerating chemicals, 100 parts cement with respect in the cement concrete is 5-15 part.
10. according to each described spray material among the above-mentioned 1-9, it is characterized in that with respect to 100 parts of cement in the cement concrete, the rapid hardening auxiliary agent is 0.05-25 part.
11., it is characterized in that the Brian specific surface area value of rapid hardening auxiliary agent is at 2000cm according to each described spray material among the above-mentioned 1-10
2More than/the g.
12., it is characterized in that the CaO in the calcium sulphoaluminate of rapid hardening auxiliary agent is 30-50 part, Al according to each described spray material among the above-mentioned 1-11
2O
3Be 40-60 part, SO
3It is 5-20 part.
13., it is characterized in that the CaO in the ca aluminosilicate of rapid hardening auxiliary agent is 20-60 part, Al according to each described spray material among the above-mentioned 1-12
2O
3Be 2-60 part, SiO
2It is 6-50 part.
14. according to each described spray material among the above-mentioned 1-13, it is characterized in that, also contain calcium sulfate.
15. spray material according to claim 14 is characterized in that, with respect to 100 parts cement in the cement concrete, calcium sulfate is 1-7 part.
16. according to each described spray material among the above-mentioned 1-15, it is characterized in that, also contain retardant.
17., it is characterized in that with respect to 100 parts cement in the cement concrete, retardant is 0.05-5 part according to above-mentioned 16 described spray material.
18. spraying coating process is characterized in that, adopts among the above-mentioned 1-17 each spray material.
19., it is characterized in that the calcium sulfate that adds liquid accelerating chemicals, rapid hardening auxiliary agent and add as required in the cement concrete that force feed comes sprays according to above-mentioned 18 described spraying coating process.
20. according to above-mentioned 18 or 19 described spraying coating process, it is characterized in that, with the rapid hardening auxiliary agent and the calcium sulfate and the cement concrete that add as required be pre-mixed, more liquid accelerating chemicals is added in the cement concrete of force feed, spray.
Embodiment
Below, the present invention is described in detail.
Cement concrete of the present invention is meant the general name that contains grout, mortar and concrete cement material." part " of the present invention or " % " are during as not specially provided for, all in mass.
Liquid accelerating chemicals in the spray material of the present invention is to contain aluminium source, sulphur source and fluorine source, better also contains the material of alkanolamine or alkali metal source etc.
There is not restriction especially for the aluminium source among the present invention (aluminium base feed), the aluminium hydroxide of available amorphousness or crystal matter, the vitriol of aluminium, aluminate, other the compound of compound, organoaluminum of inorganic aluminium and the compound of aluminium complex etc.Can use wherein a kind of or more than two kinds.Wherein, better use the vitriol of the aluminium that becomes the sulphur source in the present invention.
There is not restriction especially for sulphur source (sulphur base feed), except the sulphur of the such elementary state of sulphur or flowers of sulfur, the compounds of available sulfide, sulfuric acid or vitriol, sulfurous acid or sulphite, thiosulfuric acid or thiosulphate and organosulfur etc. can use wherein a kind of or more than two kinds.Wherein, low from solvability height, the cost that is dissolved in water, and rapid hardening performance and all good aspect consideration of state, sulfuric acid or vitriol are better.The alum class and compound that contain aluminium and alkali metal in the special handy vitriol.
Fluorine source (fluorine base feed), so long as dissolving or be scattered in the material of solvent or water does not have special restriction to this, available organofluorine compound, fluorochemical, silicofluoride and silicofluoride etc. can use wherein a kind of or more than two kinds.Wherein, the aspect that never toxicity and explosivity etc. are dangerous, cost is low and the rapid hardening performance state is good is considered, more handy fluorochemical, silicofluoride or silicofluoride.
The material that has the N-R-OH structure in the better contained more handy structural formula of alkanolamine in the liquid accelerating chemicals of the present invention.Here R is called as alkyl or allylic atomic radical.It is the atomic radical that is called as alkylidene group or arylene.For example, as alkylidene group, the group of straight chain types such as available methylene radical, ethylidene, positive propylidene has the material of branch's structure such as isopropylidene etc.As arylene, available material etc. with aromatic nucleus such as phenylene or tolyls.R can combine with nitrogen-atoms 2 above positions, and part or all of R also can be ring texture.In addition, R also can combine with a plurality of hydroxyls, can also contain carbon and water element in addition in the part of alkylidene group, for example, and sulphur, fluorine, chlorine and oxygen etc.
Above-mentioned alkanolamine is for example: thanomin, diethanolamine, trolamine, N-Mono Methyl Ethanol Amine, N, N-dimethylethanolamine, N, N-dibutyl thanomin, N-(2-amino-ethyl) thanomin, boron trifluoride trolamine or their derivative etc.In the present invention, available wherein a kind of or more than two kinds, wherein, more handy diethanolamine, N, N-dimethylethanolamine and their mixture.Special handy diethanolamine and N, the mixture of N-dimethylethanolamine.
Not having restriction especially for the better contained alkali metal source (basic metal base feed) in the liquid accelerating chemicals of the present invention, can be to contain alkali metal, i.e. the water miscible compound of lithium, sodium, potassium, rubidium or caesium.The for example oxide compound of available bases metallic element, superoxide, muriate, oxyhydroxide, nitrate, nitrite, phosphoric acid salt, silicate, aluminate, vitriol, thiosulphate, persulphate, sulfide, carbonate, supercarbonate, oxalate, borate, fluorochemical, silicate, silicofluoride, alum, metal-alcoholates salt etc. can use wherein a kind of or more than two kinds.
When modulation liquid accelerating chemicals of the present invention,, better also the raw material blended method of alkanolamine, alkali metal source or hydroxycarboxylic acid there is not special restriction for above-mentioned aluminium source, sulphur source and fluorine source.
Amount for the aluminium source in the liquid accelerating chemicals, sulphur source and fluorine source does not have special restriction, and amount is many more, and the rapid hardening performance is high more.Therefore, with respect to being converted into SO
3100 parts in sulphur source, better contain and be converted into Al
2O
3The aluminium source, the fluorine source of 2-50 part of 25-110 part.
When using alkanolamine, alkanolamine is with respect to being converted into SO
3100 parts in sulphur source, better contain 1-30 part.
When using alkali metal source, with respect to being converted into SO
3100 parts in sulphur source, better contain R
22-50 part alkali metal source that O conversion (R is a basic metal) forms.
The reason of setting for the upper limit of the amount that respectively contains composition in the liquid accelerating chemicals is: increases or reason such as permanent stability variation is considered from the viscosity of liquid, rather than from the rapid hardening performance state being caused dysgenic reason considers.
Liquid accelerating chemicals of the present invention also can contain other compositions in the scope that does not significantly reduce effect of the present invention except above composition.
In liquid accelerating chemicals of the present invention, also can contain known water miscible hydration promotor.Hydration promotor can be with mineral-type hydration promotor such as the hydration promotor of organic class of formic acid or its salt, acetate or its salt, lactic acid or its salt etc. for example, water glass, nitrate, nitrite, thiosulphate, thiocyanate-s.
The solid component concentration of liquid accelerating chemicals better is 20-60%, is more preferably 25-50%.Less than 20%, may not obtain excellent rapid hardening performance state, surpass at 60% o'clock, the viscosity height of liquid, the performance of carrying out force feed with pump may variation.
Liquid accelerating chemicals of the present invention better is acid, and below 6, the spy is 1.5-4 fortunately more fortunately for pH.
The form of liquid accelerating chemicals of the present invention is liquid, also comprises the milkiness liquid state, does not have special restriction for the size of the suspended particles in the emulsion, from the dispersiveness of suspended particles, more fortunately below the 5 μ m.
The usage quantity of liquid accelerating chemicals of the present invention with respect to 100 parts of cement in the cement concrete, better is 5-15 part, be more preferably 7-10 part.If the usage quantity of liquid accelerating chemicals is during less than 5 parts, the rapid hardening performance that may not bring into play, when surpassing 15 parts, manifesting property of longterm strength can variation.
In the present invention, there is not special restriction for the content of the cement in the cement concrete, from good manifesting property of intensity, 350kg/m
3Above usage quantity is better.As the kind of cement, available common, various portland cements such as speed is hard, hard, the middle heat of hypervelocity and low-heat; Any in the various mixed cements that fusion blast furnace slag, flying dust, limestone micropowder form in these portland cements etc.There is not special restriction for the ratio of mixture in the mixed cement and cement, also can be in order to the material that more than the ratio of JIS defined above-mentioned mixing material is mixed.
In spray material of the present invention, contain share with above-mentioned liquid accelerating chemicals, by the rapid hardening auxiliary agent at least a or that constitute more than two kinds in the material that is selected from calcium aluminate, calcium sulphoaluminate, ca aluminosilicate, alkali metal containing, calcium hydroxide and the aluminium hydroxide.By containing these rapid hardening auxiliary agents, can bring into play the rapid hardening of liquid accelerating chemicals to greatest extent.
Owing to use above-mentioned rapid hardening auxiliary agent, the concrete mobile retentivity meeting variation in basis (base) at this moment, is share retardant again.Rapid hardening auxiliary agent and retardant better are contained in the spraying that is pre-formed to the basis and use in the concrete.
Content for the rapid hardening auxiliary agent among the present invention does not have special restriction, with respect to 100 parts of cement in the cement concrete, better is that 0.05-25 part, spy are well that 0.1-15 part is comparatively suitable.For the granularity of rapid hardening auxiliary agent and the special restriction of the nothing that distributes thereof, the Brian specific surface area of its granularity (the following Brian value that also is called) is 2000cm more fortunately
2More than/the g, the spy is 3000cm fortunately
2More than/the g, comparatively suitable.
As the calcium aluminate of rapid hardening auxiliary agent, owing to be to react with liquid accelerating chemicals, with the material of manifesting property of initial strength raising, so better be with CaO raw material and Al
2O
3The material that raw material etc. mix carries out roasting in stove, carry out thermal treatments such as fusion in electric furnace, pulverizes and the material that makes.That is, CaO is write a Chinese character in simplified form into C, with Al
2O
3Writing a Chinese character in simplified form into A, for example is C
3A, C
12A
7, C
11A
7CaF
2, C
11A
7CaCl
2, CA and CA
2Deng, also can be with above-mentioned a kind of or share more than two kinds.The material that forms of basic metal such as the Na of 0.05-5%, K, Li that also can use in above-mentioned substance solid solution or contain SiO as mineralizer (ミ ネ ラ イ ザ one) less than 6%
2Material.The also available material that contains Mg and Mn.
Calcium aluminate can use amorphousness, also can use crystal matter, and two states also can be mixed in.
For the granularity of calcium aluminate and the special restriction of the nothing that distributes thereof, the Brian value is at 3000cm
2More than/the g, comparatively desirable from the viewpoint of manifesting property of initial strength, better at 5000cm
2More than/the g.Less than 3000cm
2During/g, can be able to not obtain excellent rapid hardening.
For the usage quantity indefinite of calcium aluminate, for 100 parts of cement, better be 1-10 part, be more preferably 2-5 part.During less than 1 part, can not obtain excellent rapid hardening; When surpassing 10 parts, concrete mobile retentivity may variation.
The used calcium sulphoaluminate (hereinafter referred to as CSA) of the present invention is the material that improves manifesting property of initial strength with liquid accelerating chemicals reaction.Better be to carry out in stove with CaO raw material, Al
2O
3Raw material and CaSO
4The material that raw material etc. mix carries out the thermal treatment of roasting etc., pulverizes and the material that makes, and be CaO-Al
2O
3-SO
3The mineral substance of class.
It is that CaO is 30-50 part, Al that the optimum chemical of CSA is formed
2O
3Be 40-60 part, SO
3Be 5-20 part, contain other MgO, the SiO below 10 parts in addition
2Perhaps Fe
2O
3Deng composition, also can make the basic metal solid solution.Because of showing excellent rapid hardening and manifesting property of intensity, better use hauyne (hauyne (hauyne), 3CaO3Al
2O
3CaSO
4).
For the granularity of CSA and the special restriction of the nothing that distributes, the Brian value is at 2000cm
2More than/the g, comparatively desirable from manifesting property of initial strength, better at 3000cm
2More than/the g.Less than 2000cm
2During/g, can be able to not obtain excellent rapid hardening and manifesting property of intensity.
Not having special restriction for the usage quantity of CSA, for 100 parts of cement, better is 1-20 part, is more preferably 2-10 part.Less than 1 part, may not obtain excellent rapid hardening performance state; If surpass 20 parts, the mobile retentivity of cement concrete may descend.
Being used for ca aluminosilicate of the present invention (hereinafter referred to as CAS) is by reacting the material that improves manifesting property of initial strength with liquid accelerating chemicals.Better be with CaO raw material, Al in stove
2O
3Raw material and SiO
2The material that raw material etc. mix carries out carrying out in roasting, the electric furnace thermal treatments such as fusion, pulverizing and the material that obtains.The chemical constitution of CAS is: CaO is 20-60 part, Al
2O
3Be 2-60 part, SiO
2Be 6-50 part, other also contain a kind of of iron protoxide less than 30%, ferric oxide, manganese oxide, magnesium oxide, phosphoric acid, basic metal etc. or more than two kinds.
Also can use the various Water Quenching Slag, the slow cooling slag that derive from from blast furnace and steelworks, but better use Water Quenching Slag.
For the granularity of CAS and the special restriction of the nothing that distributes, the Brian value is at 2000cm
2More than/the g,, more satisfactory from manifesting property of initial strength; Better at 3000cm
2More than/the g.Less than 2000cm
2/ g can not obtain excellent rapid hardening and manifesting property of intensity.
Not having special restriction for the usage quantity of CAS, for 100 parts of cement, better is 1-25 part, is more preferably 3-15 part.During less than 1 part, can be able to not obtain excellent rapid hardening performance state; Surpass 25 parts, the flowability of cement concrete descends.
As rapid hardening auxiliary agent of the present invention, the material that uses alkali metal containing is because will promote manifesting property of initial strength, still, as other reason, utilizes the acid liquid accelerating chemicals to make a large amount of dissolved alkali metals, from the permanent stability of liquid, is difficult.
Material (hereinafter referred to as alkaloid substance) for alkali metal containing does not have restriction especially, so long as contain alkali metal, that is, the water miscible compound of lithium, sodium, potassium, rubidium or caesium gets final product.The for example oxide compound of available bases metallic element, superoxide, muriate, oxyhydroxide, nitrate, nitrite, phosphoric acid salt, silicate, aluminate, vitriol, thiosulphate, persulphate, sulfide, carbonate, supercarbonate, oxalate, borate, fluorochemical, silicate, silicofluoride, alum, exsiccated alum or metal-alcoholates salt etc. can use wherein a kind of or more than two kinds.
There is not special restriction for the usage quantity of alkaline matter, for 100 parts cement, with R
2O (the R: basic metal), better be 0.05-3 part that converts.During less than 0.05 part, can be able to not obtain excellent rapid hardening performance state; When surpassing 3 parts, concrete mobile retentivity descends.
As the calcium hydroxide of rapid hardening auxiliary agent, be the material of the slaked lime that generated when containing unslaked lime and carbide of calcium hydration, make water in nature at concrete, the result can use and make unslaked lime that calcium hydroxide generates etc. in a large number; Perhaps itself and calcium hydroxide are share.Crystalline form for calcium hydroxide does not have special restriction.
As the aluminium hydroxide of rapid hardening auxiliary agent, be Al (OH)
3Perhaps AlO (OH) nH
2The material of O etc.Aluminium hydroxide can be with crystalloid or amorphous material, can use anyly, better uses amorphous aluminium hydroxide.
Fines content for calcium hydroxide and aluminium hydroxide does not have special restriction, and the Brian value is 4000cm more fortunately
2More than/the g, better at 8000cm
2More than/the g.Less than 4000cm
2/ g when spraying, may not obtain the excellent tack attached to massif.
Not having special restriction for the usage quantity of calcium hydroxide and/or aluminium hydroxide, for 100 parts of cement, better is 0.5-5 part, is more preferably 0.8-3 part.Less than 0.5 part,, may not obtain the excellent tack that is attached on the massif in when spraying; When surpassing 5 parts, may damage manifesting property of longterm strength.
In spray material of the present invention, better contain retardant.Relevant retardant is by suppressing the general name of the material of hydration with cement mixing, is the material for keeping concrete flowability to use.Probably can use the retardant of organic retardant and inorganics.
As the concrete example of organism retardant, polymer organic acid or its salt such as available (1) lignin sulfonic acid, humic acid, tannic acid; (2) hydroxycarboxylic acid or its salt such as citric acid, oxysuccinic acid, tartrate, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, toxilic acid, fumaric acid, phthalic acid, arabonic acid, glucose enanthic acid, glyconic acid; Ketone acid or its salt of (3) two keto-earboxylic acids or urea etc.; (4) aminocarboxylic acid or its salt of L-glutamic acid etc.; (5) polyalcohols; (6) monoses such as glucose, fructose, glucono-lactone, semi-lactosi, sucrose, wood sugar, Xylitol, ア PVC ト one ス, ribose, isomerized sugar; The carbohydrate of two-three carbohydrate oligose etc.; (7) glycitols such as polyoses such as dextrin, hemicellulose, inulin, alginic acid, xylan, dextran etc. and (8) Sorbitol Powder etc.
The concrete example of inorganics retardant is: the mineral acid of phosphoric acid or etching acid etc.; Fluorine-containing mineral such as silicofluorides such as phosphoric acid salt, zinc oxide, plumbous oxide, boric acid, magnesium silicofluoride, sodium silicofluoride or sodium aluminum fluoride, calcium chloroaluminate etc., in the present invention, in the scope that does not hinder purpose of the present invention, can use a kind of in above-mentioned or more than two kinds.
Do not have special restriction for the usage quantity of retardant,, better use 0.05-5 part for 100 parts cement.Less than 0.05 part, may mustn't go to concrete enough mobile retentivities; When surpassing 5 parts, may not obtain enough manifesting property of intensity.
In spray material of the present invention, also can add ideal calcium sulfate as intensity improvement agent.Calcium sulfate can use dehydrated gyp-, semi-hydrated gypsum or dihydrate gypsum etc., can use wherein a kind of or more than two kinds.
Crystalline form for calcium sulfate does not have special restriction, available alpha semi-hydrated gypsum, beta-type semi-hydrated gypsum, I type dehydrated gyp-, II type dehydrated gyp-and III dehydrated gyp-etc.
These calcium sulfate comprise the gypsum of natural output, get rid of the secondary dehydrated gyp-that generates of gypsum, hydrofluoric acid etc. as the industrial by-products gained.
The granularity of calcium sulfate, the Brian value is at 3000cm
2More than/the g,, comparatively desirable from manifesting property of intensity.
Not having special restriction for the usage quantity of calcium sulfate, for 100 parts cement, better is 1-7 part, is more preferably 1.5-5 part.During less than 1 part, can not obtain excellent manifesting property of intensity; When surpassing 7 parts, overplumping, strength degradation.
In spray material of the present invention, except containing aggregates such as above-mentioned each material, sand, gravel, substantially do not hinder in the scope of purpose of the present invention, also can contain mixing material or mixtures such as siliceous powder, water reducer, AE agent, tackifier and fiber.
Siliceous powder can use industrial by-products such as silicon-dioxide smog, flying dust, pyrolysis method, colloidal silica, settleability silicon-dioxide isogel class silicon-dioxide etc.Can use a kind of in the silica material wherein or more than two kinds.
Water reducer can use for example all known water reducers such as lignin sulfonic acid class, naphthene sulfonic acid class, poly carboxylic acid.
The AE agent can prevent that concrete from freezing.
Tackifier are that the material that improves aggregate, grout or other additive is difficult for material separatory, cellulose families such as for example available methylcellulose gum, carboxy methyl cellulose, ether of cellulose; Polymkeric substance such as polyethylene oxide, poly(propylene oxide), polybutylene oxide; Multipolymer with vinylformic acid, methacrylic acid, ester is acrylic polymers of principal constituent etc.
Fiber from the shock-resistance and the elastic aspect that can improve cement concrete, uses, and also can use any in inanimate matter or the organic matter.
As the fiber of inanimate matter, useable glass fiber, carbon fiber, aminanthine, asbestos, ceramic fiber, steel fiber etc.
As organic fiber, available vinylon fiber, polyethylene fibre, polypropylene fibre, polyacrylic fibre, cellulosic fibre, polyvinyl alcohol fiber, tynex, paper pulp, fiber crops, wolline, wood chip etc.From the economy aspect, more handy steel fiber and vinylon fiber wherein.
Staple length is from viewpoints such as coming property of force feed and Combination, more fortunately below the 50mm, better at 5-30mm.There is not special restriction for the aspect ratio of fiber.
With the spray material of the present invention method on the domatic and tunnel of spraying to can be the dry type of carrying out usually or any method in the wet type, considers more handy wet type spray technology wherein from producing the dust aspect less.
In the present invention, when being blended in liquid accelerator in the cement concrete, mix before facing spraying more fortunately.Specifically, better force feed is come and add liquid accelerator, rapid hardening auxiliary agent and other additive as required in the cement concrete that comes, fix in 10 seconds to the time that this rapid hardening cement concrete sprays out, better in 2 seconds.
Liquid accelerator of the present invention heats in 20 ℃-90 ℃ the scope more fortunately, and it is mixed with cement concrete, further improves rapid hardening.
Flowability value and flow valuve for the cement concrete of spraying usefulness of the present invention do not have special restriction, and in the syntagmatic category of known construction system, if no problem is constructed, what value can be used.
Embodiment 1
Adopting cement/sand is 1/2.5, and W/C is 45% proportioning, in 100 parts of cement, cooperates 3 parts calcium aluminate (hereinafter referred to as CA) a, uses water reducer that the flowability value is adjusted into about 15cm, makes mortar.
In 100 parts the cement in the mortar that modulates, 10 parts of the liquid accelerating chemicalss shown in the mixture table 1, pack into framed in, measure the anti-intrusion value of Pu Shi 20 ℃ of test ambient temperature.The result is as shown in table 1.
For relatively,, test too for the system of not using CAa.
(materials used)
Raw material A: aluminium source (the pure pharmaceutical worker's industry of Tai-Ace S 150 8 hydrates and light company makes 1 grade of chemical reagent).
Raw material B: aluminium source (the pure pharmaceutical worker's industry of aluminium hydroxide and light company makes 1 grade of chemical reagent).
Raw material C: aluminium source (the pure pharmaceutical worker's industry of sodium aluminate and light company makes 1 grade of chemical reagent).
Raw material D: sulphur source (the pure pharmaceutical worker's industry of sulfuric acid and light company makes 1 grade of chemical reagent).
Raw material E: fluorine source (the pure pharmaceutical worker's industry of Calcium Fluoride (Fluorspan) and light company makes 1 grade of chemical reagent).
Raw material F: fluorine source (the pure pharmaceutical worker's industry of Sodium Fluoride and light company makes 1 grade of chemical reagent).
Raw material G: fluorine source (the pure pharmaceutical worker's industry of aluminum fluoride and light company makes 1 grade of chemical reagent).
Raw material H: fluorine source (the pure pharmaceutical worker's industry of Potassium monofluoride and light company makes 1 grade of chemical reagent).
Raw material I: fluorine source (the pure pharmaceutical worker's industry of sodium aluminum fluoride and light company makes 1 grade of chemical reagent).
Raw material J: alkanolamine (the pure pharmaceutical worker's industry of diethanolamine and light company makes 1 grade of chemical reagent).
Raw material K: alkanolamine (N, the pure pharmaceutical worker's industry of N-dimethylethanolamine and light company makes 1 grade of chemical reagent).
Raw material L: alkali metal source (the pure pharmaceutical worker's industry of yellow soda ash and light company makes 1 grade of chemical reagent).
Raw material M: alkali metal source (the pure pharmaceutical worker's industry of potassium hydroxide and light company makes 1 grade of chemical reagent).
Raw material N: alkali metal source (the pure pharmaceutical worker's industry of sodium hydroxide and light company makes 1 grade of chemical reagent).
Raw material O: alkali metal source (the pure pharmaceutical worker's industry of sodium aluminate and light company makes 1 grade of chemical reagent).
Liquid accelerating chemicals: according to elementary composition shown in the table 1 each raw material is calculated mixing, with ball mill 50 parts in mixture and the water that makes is mixed for 50 parts, 80 ℃ were stirred 3 hours down.
Cement: normal portland cement, the commodity that sell the market, proportion 3.16.
CAa: with mol ratio 1: 1 with CA, CaO raw material, Al
2O
3Mix to pulverize, carry out 3 hours the formed material of roasting with electric furnace under 1350 ℃, the Brian value is 6000cm
2/ g.
Sand: river sand, proportion 2.62 are produced in Ju river, Nigata county.
Water reducer: polycarboxylic acid high-performance water reducer (commodity that sell the market).
Water: tap water
(measuring method)
The anti-intrusion value of Pu Shi: measure according to JSCE D-102-1999, material age is 10 minutes.
Embodiment 2
In the cement of the liquid accelerating chemicals to 100 that adds table 1 test number 1-10 with the amount shown in the table 2 part, carry out similarly to Example 1.The result is as shown in table 2.
Embodiment 3
Except in 100 parts of cement, adding CA, alkaline matter, calcium hydroxide and the aluminium hydroxide shown in 0.3 part of retardant, the table 3, use is the liquid accelerating chemicals of 10 parts table 1 test number 1-10 for 100 parts cement, beyond the modulation mortar, carry out similarly to Example 1.The result is as shown in table 3.
(materials used)
CA beyond the CAe uses following material: will each raw material be mixed with the regulation ratio down at 1350 ℃ with electric furnace and pulverize the 3 hours prepared materials of material roasting that form.CAe is 1600 ℃ of following roastings, the sudden cold amorphousness material that forms.The Brian value all is adjusted to 6000cm
2/ g.
CAb:C
12A
7, the Brian value is 6000cm
2/ g.
CAc:C
11A
7CaCl
2, the Brian value is 6000cm
2/ g.
CAd:C
3A, the Brian value is 6000cm
2/ g.
CAe:C
12A
7Glass, Brian value are 6000cm
2/ g.
Alkaline matter A: the pure pharmaceutical worker's industry of yellow soda ash and light company makes 1 grade of chemical reagent.
Alkaline matter B: the pure pharmaceutical worker's industry of sodium aluminate and light company makes 1 grade of chemical reagent.
Alkaline matter C: the pure pharmaceutical worker's industry of potassium hydroxide and light company makes 1 grade of chemical reagent.
Calcium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 13000cm
2/ g.
Aluminium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 18000cm
2/ g.
Retardant: the pure pharmaceutical worker's industry of sodium tartrate and light company makes 1 grade of chemical reagent.
Embodiment 4
Except the CSA with the amount shown in the table 4 is engaged in 100 parts of the cement, in 100 parts of cement in the mortar that modulates, mix beyond the liquid accelerating chemicals as shown in table 4, test similarly to Example 1, the result is as shown in table 4.
For relatively, the system of not using CSA is tested too.
(materials used)
CSA: with mol ratio 3: 3: 1 with hauyne (hauyne), CaO raw material, Al
2O
3Raw material and CaSO
4Raw material mixes, and pulverizes the material that made in 3 hours 1350 ℃ of following roastings with electric furnace.The Brian value is 4000cm
2/ g.
Embodiment 5
Except the liquid accelerating chemicals with table 4 test number 4-10 is added in 100 parts the cement with the amount shown in the table 5, measure similarly to Example 1.The result is as shown in table 5.
Embodiment 6
Except in 100 parts cement, add 0.15 part retardant, CSA, alkaline matter, calcium hydroxide and aluminium hydroxide as shown in table 6, use is beyond 10 parts the liquid accelerating chemicals of test number 4-10 of table 4 for 100 parts cement, test similarly to Example 1, the result is as shown in table 6.
(materials used)
Alkaline matter A: the pure pharmaceutical worker's industry of yellow soda ash and light company makes 1 grade of chemical reagent.
Alkaline matter B: the pure pharmaceutical worker's industry of potassium aluminate and light company makes 1 grade of chemical reagent.
Alkaline matter C: the pure pharmaceutical worker's industry of potassium hydroxide and light company makes 1 grade of chemical reagent.
Calcium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 13000cm
2/ g.
Aluminium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 18000cm
2/ g.
Retardant: the pure pharmaceutical worker's industry of Trisodium Citrate and light company makes 1 grade of chemical reagent.
Embodiment 7
Except in 100 parts cement, add beyond 0.05 part the retardant and CAS, calcium hydroxide and calcium sulfate as shown in table 7, test similarly to Example 6.The result is as shown in table 7.
(materials used)
CASa:CaO45%, Al
2O
342%, SiO
213%, Brian value 5000cm
2/ g.
CASb:CaO51%, Al
2O
331%, SiO
218%, Brian value 5000cm
2/ g.
CASc:CaO41%, Al
2O
337%, SiO
222%, Brian value 5000cm
2/ g.
Calcium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 13000cm
2/ g.
Calcium sulfate: natural dehydrated gyp-, Brian value 4300cm
2/ g.
Alkaline matter: the pure pharmaceutical worker's industry of yellow soda ash and light company makes 1 grade of chemical reagent.
Retardant: the pure pharmaceutical worker's industry of gluconic acid sodium salt and light company makes 1 grade of chemical reagent.
Embodiment 8
Except in 100 parts cement, add 3 parts calcium sulfate, in 100 parts the cement in the mortar that modulates, mix 10 parts of liquid accelerating chemicalss as shown in table 7, beyond compressive strength is measured, test similarly to Example 1.The result is as shown in table 8.
For relatively, test too for the system of not using calcium sulfate.
(materials used)
Calcium sulfate: natural dehydrated gyp-, Brian value 4300cm
2/ g.
(measuring method)
Compressive strength:, measured in 24 hours with material age according to JIS R5201.
Embodiment 9
Except in 100 parts of cement, add the liquid accelerating chemicals of the test number 8-10 of table 8 with amount as shown in table 9, measure beyond the anti-intrusion value of Pu Shi, test similarly to Example 1.The result is as shown in table 9.
Embodiment 10
Except in 100 parts of cement, add 0.3 part retardant, calcium sulfate, calcium aluminate and the alkaline matter of the amount shown in the table 10, interpolation is beyond 10 parts the liquid accelerating chemicals of test number 8-10 of table 8, to test similarly to Example 1 for 100 parts cement, and the result is as shown in table 10.
(materials used)
Calcium aluminate: C
12A
7Form amorphousness, Brian value 6000cm
2/ g.
Alkaline matter: the pure pharmaceutical worker's industry of sodium aluminate and light company makes 1 grade of chemical reagent.
Retardant: the pure pharmaceutical worker's industry of sodium tartrate and light company makes 1 grade of chemical reagent.
Embodiment 11
Except in 100 parts of cement, cooperate the alkaline matter of the amount shown in the table 11, in 100 parts of cement in the mortar that modulates, beyond 10 parts of the liquid accelerating chemicalss shown in the mixture table 11, test similarly to Example 1.The result is as shown in table 11.
For relatively,, test too not using the system of alkaline matter.
(materials used)
Alkaline matter D: the pure pharmaceutical worker's industry of sodium aluminate and light company makes 1 grade of chemical reagent.
Embodiment 12
Except in 100 parts cement, add with the amount shown in the table 12 beyond the liquid accelerating chemicals of test number 11-10 of table 11, test similarly to Example 1.The result is as shown in table 12.
Embodiment 13
Except in 100 parts of cement, add 0.15 part retardant, the alkaline matter shown in the table 13, calcium hydroxide, aluminium hydroxide and calcium sulfate, interpolation is beyond 10 parts the liquid accelerating chemicals of test number 11-10 of table 11, to test similarly to Example 1 for 100 parts cement.The result is as shown in table 13.
(materials used)
Alkaline matter E: the pure pharmaceutical worker's industry of water glass and light company makes 1 grade of chemical reagent.
Retardant: the pure pharmaceutical worker's industry of citric acid and light company makes 1 grade of chemical reagent.
Calcium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 13000cm
2/ g.
Aluminium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 18000cm
2/ g.
Calcium sulfate: the pure pharmaceutical worker's industry of anhydrous calciumsulphate and light company makes 1 grade of chemical reagent, Brian value 7000cm
2/ g.
Embodiment 14
Except in 100 parts of cement, cooperate the calcium hydroxide shown in the table 14, in 100 parts the cement in the mortar that modulates, beyond 10 parts of the liquid accelerating chemicalss shown in the mixture table 14, test similarly to Example 1, the result is as shown in table 14.
For relatively,, test too not using the system of calcium hydroxide.
(materials used)
Calcium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 13000cm
2/ g.
Embodiment 15
Except in 100 parts cement, add with the amount shown in the table 15 beyond the liquid accelerating chemicals of table 14 test number 14-10, test similarly to Example 1.The result is as shown in Table 15.
Embodiment 16
Except in 100 parts cement, add 0.15 part retardant and the calcium hydroxide shown in the table 16, aluminium hydroxide and calcium sulfate, use is beyond 10 parts the liquid accelerating chemicals of test number 14-10 of table 14, to test similarly to Example 1 for 100 parts cement.The result is shown in table 16.
(materials used)
Calcium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 13000cm
2/ g.
Aluminium hydroxide: and the pure pharmaceutical worker's industry of light company makes 1 grade of chemical reagent, Brian value 18000cm
2/ g.
Calcium sulfate: natural dehydrated gyp-, Brian value 4300cm
2/ g.
Retardant: the pure pharmaceutical worker's industry of gluconic acid sodium salt and light company makes 1 grade of chemical reagent.
The possibility of industrial utilization
Spray material of the present invention, because rapid hardening and tack are all good, alkali number is few, manifesting property of initial strength is strong, so by use adopting the spraying coating process of above-mentioned spray material, in the digging operation in the tunnel of domatic or road, railway or catchwater etc. etc. etc., can prevent caving in of massif conscientiously, in the time of also can preventing dense spraying, the danger of peeling off.
Disclosing in the specification sheets of the present invention is incorporated in the content as the whole specification sheetss of following Japan's special permission application of the application's basis for priority:
(1) special permission application 2003-295994 number (applying for to the Japan special permission Room) on August 20th, 2003
(1) special permission application 2003-295995 number (applying for to the Japan special permission Room) on August 20th, 2003
(1) special permission application 2003-296169 number (applying for to the Japan special permission Room) on August 20th, 2003
(1) special permission application 2003-296170 number (applying for to the Japan special permission Room) on August 20th, 2003
(1) special permission application 2003-296171 number (applying for to the Japan special permission Room) on August 20th, 2003
Table 1
| Test number | Liquid accelerating chemicals composition | Liquid accelerating chemicals raw material | CAa | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks | ||||
| Al 2O 3 | SO 3 | F | Raw material J | Raw material L | |||||
| 1-1 1-2 1-3 1-4 | 0 25 60 110 | 100 100 100 100 | 15 15 15 15 | - - - - | - - - - | D、E A、D、E A、B、E A、B、E | 3 3 3 3 | 2.9 16.1 18.1 20.8 | Comparative example EXAMPLE Example embodiment |
| 1-5 1-6 1-3 1-7 | 60 60 60 60 | 100 100 100 100 | 0 2 15 50 | - - - - | - - - - | A、B A、B、E A、B、E A、B、E | 3 3 3 3 | 4.5 9.5 18.1 21.4 | Comparative example EXAMPLE Example embodiment |
| 1-8 1-9 1-10 | 60 60 60 | 0 100 100 | 15 15 15 | - - 10 | - - - | B、E A、B、E A、B、E、J | 3 0 3 | 4.4 13.4 21.0 | Comparative example comparative example embodiment |
| 1-11 1-12 1-13 1-14 | 60 60 60 60 | 100 100 100 100 | 15 15 15 15 | 10 - 10 10 | 2 15 15 50 | A、B、E、J、L A、B、E、L A、B、E、J、L A、B、E、J、L | 3 3 3 3 | 22.3 20.2 24.6 26.1 | The EXAMPLE Example EXAMPLE Example |
Liquid accelerating chemicals composition is (part), and CAa is for 100 parts of cement (part), and test number 1-10,1-11,1-13,1-14 all share 10 parts raw material J, and test number 1-11-1-14 all share raw material L, and raw material L usage quantity is with R
2O converts and forms, for 100 parts SO
3(part).The pH of all liquid accelerating chemicalss is below 6.
Table 2
| Test number | Liquid accelerating chemicals | Anti-(the N/mm that invades of Pu Shi 2) | Remarks |
| 2-1 1-10 2-2 | 5 10 15 | 5.1 21.0 30.7 | EXAMPLE Example embodiment |
Liquid accelerating chemicals is for 100 parts of cement (part)
Table 3
| Test number | CA | Alkaline matter | Calcium hydroxide | Aluminium hydroxide | The anti-intrusion value of Pu Shi (N/mm 2) | Each is annotated |
| 3-1 3-2 3-3 1-10 3-4 3-5 | - 0 a 1 a 2 a 3 a 5 a 10 | -0.0 -0.0 -0.0 -0.0 -0.0 -0.0 | 0.0 0.0 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 0.0 0.0 | 14.2 16.3 19.4 21.0 25.6 30.9 | Comparative example EXAMPLE Example EXAMPLE Example embodiment |
| 3-6 3-7 3-8 | a 3 a 3 a 3 | A 0.1 A 0.3 A 2.0 | 0.0 0.0 0.0 | 0.0 0.0 0.0 | 24.5 27.8 29.2 | EXAMPLE Example embodiment |
| 3-9 3-10 | a 3 a 3 | B 0.3 C 0.3 | 0.0 0.0 | 0.0 0.0 | 27.3 26.9 | EXAMPLE Example |
| 3-11 3-12 3-13 3-14 | a 3 a 3 a 3 a 3 | A 0.3 A 0.3 A 0.3 A 0.3 | 0.5 0.8 3.0 5.0 | 0.0 0.0 0.0 0.0 | 28.5 29.2 30.6 31.3 | The EXAMPLE Example EXAMPLE Example |
| 3-15 3-16 | a 3 a 3 | A 0.3 A 0.3 | 0.0 0.0 | 0.5 3.0 | 29.2 32.1 | EXAMPLE Example |
| 3-17 3-18 3-19 3-20 3-21 | a 3 b 3 c 3 d 3 e 3 | A 0.3 A 0.3 A 0.3 A 0.3 A 0.3 | 1.5 1.5 1.5 1.5 1.5 | 1.5 1.5 1.5 1.5 1.5 | 31.4 31.1 29.5 32.3 33.5 | EXAMPLE Example EXAMPLE Example embodiment |
CA, calcium hydroxide and aluminium hydroxide are for 100 parts of cement (part), and the usage quantity of the material of alkalescence is with R
2O converts, for (part) of 100 parts of cement.
Table 4
| Test number | Liquid accelerating chemicals composition | Liquid accelerating chemicals raw material | CS A | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks | ||||
| Al 2O 3 | SO 3 | F | Raw material J | Raw material L | |||||
| 4-1 4-2 4-3 4-4 | 0 25 60 110 | 100 100 100 100 | 15 15 15 15 | - - - - | - - - - | D、F A、D、F A、B、F A、B、F | 3 3 3 3 | 2.1 10.2 20.4 24.3 | Comparative example EXAMPLE Example embodiment |
| 4-5 4-6 4-3 4-7 | 60 60 60 60 | 100 100 100 100 | 0 2 15 50 | - - - - | - - - - | A、B A、B、F A、B、F A、B、F | 3 3 3 3 | 6.6 9.8 20.4 23.5 | Comparative example EXAMPLE Example embodiment |
| 4-8 4-9 4-1 | 60 60 60 | 0 100 100 | 15 15 15 | - - 10 | - - - | B、F A、B、F A、B、F、J | 3 0 3 | 5.4 13.0 24.7 | Comparative example comparative example embodiment |
| 4-11 4-12 4-13 4-14 | 60 60 60 60 | 100 100 100 100 | 15 15 15 15 | 10 - 10 10 | 2 15 15 50 | A、b、F、J、L A、b、F、L A、b、F、J、L A、b、F、J、L | 3 3 3 3 | 25.1 23.3 27.6 30.2 | The EXAMPLE Example EXAMPLE Example |
Liquid accelerating chemicals composition is (part), and CSA is for 100 parts of cement (part), and test number 4-10,4-11,4-13,4-14 all share 10 parts raw material J, and test number 4-11-4-14 all share raw material L, and raw material L usage quantity is with R
2O converts and forms, for 100 parts SO
3(part).The pH of all liquid accelerating chemicalss is below 6.
Table 5
| Test number | Liquid accelerating chemicals | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 5-1 4-10 5-2 | 5 10 15 | 6.3 24.7 28.9 | EXAMPLE Example embodiment |
Liquid accelerating chemicals is for 100 parts of cement (part)
Table 6
| Test number | CA | Alkaline matter | Calcium hydroxide | Aluminium hydroxide | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 6-1 6-2 6-3 6-4 | 1 2 10 20 | -0.0 -0.0 -0.0 -0.0 | 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 | 24.8 25.5 28.9 34.5 | The EXAMPLE Example EXAMPLE Example |
| 6-5 6-6 6-7 6-8 | 3 3 3 3 | A 0.05 A 0.1 A 2.0 A 3.0 | 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 | 28.1 29.8 31.1 33.4 | The EXAMPLE Example EXAMPLE Example |
| 6-9 6-10 | 3 3 | B 0.3 C 0.3 | 0.0 0.0 | 0.0 0.0 | 30.8 29.7 | EXAMPLE Example |
| 6-11 6-12 6-13 | 3 3 3 | A 0.3 A 0.3 A 0.3 | 3.0 0.0 1.5 | 0.0 3.0 1.5 | 31.2 33.4 32.3 | EXAMPLE Example embodiment |
CSA, calcium hydroxide and aluminium hydroxide are for 100 parts of cement (part), and the usage quantity of alkaline matter is with R
2O converts and forms, for (part) of 100 parts of cement.
Table 7
| Test number | CAS | Calcium hydroxide | Calcium sulfate | Alkaline matter | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 7-1 7-2 7-3 7-4 7-5 | a1 a3 a5 a15 a25 | 0.0 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 0.0 | 22.1 23.7 25.3 30.5 35.6 | EXAMPLE Example EXAMPLE Example embodiment |
| 7-6 7-7 7-8 7-9 7-10 | a5 a5 a5 a5 a5 | 0.5 0.8 1.5 3.0 5.0 | 0.0 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 0.0 | 26.1 27.2 28.9 30.1 33.5 | EXAMPLE Example EXAMPLE Example embodiment |
| 7-11 7-12 7-13 7-14 7-15 | a5 a5 a5 a5 a5 | 1.5 1.5 1.5 1.5 1.5 | 1.0 1.5 3.0 5.0 7.0 | 0.0 0.0 0.0 0.0 0.0 | 29.4 30.3 31.1 28.5 27.7 | EXAMPLE Example EXAMPLE Example embodiment |
| 7-16 7-17 7-18 7-19 7-20 | a5 a5 a5 a5 a5 | 1.5 1.5 1.5 1.5 1.5 | 3.0 3.0 3.0 3.0 3.0 | 0.05 0.1 0.3 2.0 3.0 | 32.2 33.1 34.5 33.3 31.1 | EXAMPLE Example EXAMPLE Example embodiment |
| 7-21 7-22 | b5 c5 | 0.0 0.0 | 0.0 0.0 | 0.0 0.0 | 24.4 23.1 | EXAMPLE Example |
All for 100 parts of cement (part), the usage quantity of alkaline matter is with R for CAS, calcium hydroxide and calcium sulfate
2O converts and forms, for (part) of 100 parts of cement.
Table 8
| Test number | Liquid accelerating chemicals composition | Liquid accelerating chemicals raw material | Calcium sulfate | The anti-intrusion value of Pu Shi (N/mm 2) | Compressive strength | Remarks | ||||
| Al 2O 3 | SO 3 | F | Raw material J | Raw material M | ||||||
| 8-1 8-2 8-3 8-4 | 0 25 60 110 | 100 100 100 100 | 15 15 15 15 | - - - - | - - - - | D、G A、D、G A、B、G A、B、G | 3 3 3 3 | 1.2 7.6 17.4 18.1 | 11.4 13.9 12.5 11.1 | Comparative example EXAMPLE Example embodiment |
| 8-5 8-6 8-3 8-7 | 60 60 60 60 | 100 100 100 100 | 0 2 15 50 | - - - - | - - - - | A、B A、B、G A、B、G A、B、G | 3 3 3 3 | 2.3 6.9 17.4 18.5 | 13.5 13.1 12.5 9.8 | Comparative example EXAMPLE Example embodiment |
| 8-8 8-9 8-10 | 60 60 60 | 0 100 100 | 15 15 15 | - - 10 | - - - | B、G A、B、G A、B、G、J | 3 0 3 | 3.8 13.5 18.3 | 10.1 5.2 10.3 | Comparative example comparative example embodiment |
| 8-11 8-12 8-13 8-14 | 60 60 60 60 | 100 100 100 100 | 15 15 15 15 | 10 - 10 10 | 2 15 15 50 | A、B、G、J、M A、B、G、M A、B、G、J、M A、B、G、J、M | 3 3 3 3 | 20.1 19.5 22.7 23.9 | 9.9 10.8 8.8 8.2 | The EXAMPLE Example EXAMPLE Example |
Liquid accelerating chemicals composition (part), calcium sulfate are all for 100 parts of cement (part), and anti-intrusion value of Pu Shi and compressive strength all are (N/mm
2), test number 8-10,8-11,8-13,8-14 all share 10 parts raw material J, and test number 8-11-8-14 all share raw material M, and raw material M usage quantity is with R
2O converts and forms, for 100 parts SO
3(part).The pH of all liquid accelerating chemicalss is below 6.
Table 9
| Test number | Liquid accelerating chemicals | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 9-1 8-10 9-2 | 5 10 15 | 5.3 18.3 25.1 | EXAMPLE Example embodiment |
Liquid accelerating chemicals is for 100 parts of cement (part)
Table 10
| Test number | Calcium sulfate | Calcium aluminate | Alkaline matter | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 10-1 10-2 10-3 10-4 10-5 | 1.0 1.5 3.0 5.0 7.0 | 0.0 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 0.0 | 19.4 19.1 18.9 18.5 17.5 | EXAMPLE Example EXAMPLE Example embodiment |
| 10-6 10-7 10-8 10-9 10-10 | 3.0 3.0 3.0 3.0 3.0 | 1.0 2.0 3.0 5.0 10.0 | 0.0 0.0 0.0 0.0 0.0 | 20.1 21.9 23.3 26.6 30.3 | EXAMPLE Example EXAMPLE Example embodiment |
| 10-11 10-12 10-13 10-14 10-15 | 3.0 3.0 3.0 3.0 3.0 | 3.0 3.0 3.0 3.0 3.0 | 0.05 0.1 0.3 2.0 3.0 | 25.1 27.2 28.8 29.3 30.2 | EXAMPLE Example EXAMPLE Example embodiment |
Calcium sulfate and calcium aluminate all are (parts) for 100 parts cement, and the usage quantity of alkaline matter is with R
2O converts and forms, for (part) of 100 parts of cement.
Table 11
| Test number | Liquid accelerating chemicals composition | Liquid accelerating chemicals raw material | Alkaline matter | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks | ||||
| Al 2O 3 | SO 3 | F | Raw material J | Raw material N | |||||
| 11-1 11-2 11-3 11-4 | 0 25 60 110 | 100 100 100 100 | 15 15 15 15 | - - - - | - - - - | C、H A、D、H A、B、H A、B、H | D0.3 D0.3 D0.3 D0.3 | 1.9 12.2 21.6 23.4 | Comparative example EXAMPLE Example embodiment |
| 11-5 11-6 11-3 11-7 | 60 60 60 60 | 100 100 100 100 | 0 2 15 50 | - - - - | - - - - | A、B A、B、H A、B、H A、B、H | D0.3 D0.3 D0.3 D0.3 | 4.2 10.8 21.6 22.8 | Comparative example EXAMPLE Example embodiment |
| 11-8 11-9 11-10 | 60 60 60 | 0 100 100 | 15 - 15 | - - 10 | - - | B、H A、B、H A、B、H、J | D0.3 -0.0 D0.3 | 3.3 12.9 25.1 | Comparative example comparative example embodiment |
| 11-11 11-12 11-13 11-14 | 60 60 60 60 | 100 100 100 100 | 15 15 15 15 | 10 - 10 10 | 2 15 15 50 | A、B、H、J、N A、B、H、N A、B、H、J、N A、B、H、J、N | D0.3 D0.3 D0.3 D0.3 | 26.1 24.3 28.1 31.1 | The EXAMPLE Example EXAMPLE Example |
Liquid accelerating chemicals composition (part), alkaline matter are all for 100 parts of cement (part), and the anti-intrusion value of Pu Shi is (N/mm
2), test number 11-10,11-11,11-13,11-14 all share 10 parts raw material J, and test number 11-11-11-14 all share raw material N, and raw material N usage quantity is with R
2O converts and forms, for 100 parts SO
3(part).The pH of all liquid accelerating chemicalss is below 6.
Table 12
| Test number | Liquid accelerating chemicals | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 12-1 11-10 12-2 | 5 10 15 | 5.3 25.1 31.9 | EXAMPLE Example embodiment |
Table 13
| Test number | Alkaline matter | Calcium hydroxide | Aluminium hydroxide | Calcium sulfate | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 13-1 13-2 13-3 13-4 | D0.05 D0.1 D0.3 D3.0 | 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 | 18.7 20.1 23.5 24.2 | The EXAMPLE Example EXAMPLE Example |
| 13-5 13-6 | E0.3 C0.3 | 0.0 0.0 | 0.0 0.0 | 0.0 0.0 | 22.1 21.4 | EXAMPLE Example |
| 13-7 13-8 13-9 13-10 | D0.3 D0.3 D0.3 D0.3 | 0.5 0.8 3.0 5.0 | 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 | 24.2 25.3 26.1 25.7 | The EXAMPLE Example EXAMPLE Example |
| 13-11 13-12 13-13 13-14 | D0.3 D0.3 D0.3 D0.3 | 0.0 0.0 0.0 0.0 | 0.5 0.8 3.0 5.0 | 0.0 0.0 0.0 0.0 | 25.5 27.8 32.5 34.8 | The EXAMPLE Example EXAMPLE Example |
| 13-15 13-16 13-17 13-18 13-19 13-20 | D0.3 D0.3 D0.3 D0.3 D0.3 D0.3 | 1.5 1.5 1.5 1.5 1.5 1.5 | 1.5 1.5 1.5 1.5 1.5 1.5 | 0.0 1.0 1.5 4.0 5.0 7.0 | 30.7 31.4 32.8 32.2 31.0 30.1 | EXAMPLE Example EXAMPLE Example EXAMPLE Example |
Calcium hydroxide, aluminium hydroxide and calcium sulfate all are (part), and the usage quantity of alkaline matter is with R
2O converts and forms, for (part) of 100 parts of cement.
Table 14
| Test number | Liquid accelerating chemicals composition | Liquid accelerating chemicals raw material | Calcium hydroxide | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks | ||||
| Al 2O 3 | SO 3 | F | Raw material K | Raw material O | |||||
| 14-1 14-2 14-3 14-4 | 0 25 60 110 | 100 100 100 100 | 15 15 15 15 | - - - - | - - - - | D、I A、D、I A、B、I A、B、I | 3 3 3 3 | 1.2 9.1 18.5 21.2 | Comparative example EXAMPLE Example embodiment |
| 14-5 14-6 14-3 14-7 | 60 60 60 60 | 100 100 100 100 | 0 2 15 50 | - - - - | - - - - | A、B A、B、I A、B、I A、B、I | 3 3 3 3 | 5.1 8.2 18.5 19.3 | Comparative example EXAMPLE Example embodiment |
| 14-8 14-9 14-10 | 60 60 60 | 0 100 100 | 15 15 15 | - - 10 | - - - | B、I A、B、I A、B、I、K | 3 0 3 | 4.2 13.3 22.1 | Comparative example comparative example embodiment |
| 14-11 14-12 14-13 14-14 | 60 60 60 60 | 100 100 100 100 | 15 15 15 15 | 10 - 10 10 | 2 15 15 50 | A、B、I、K、O A、B、I、K、O A、B、I、K、O A、B、I、K、O | 3 3 3 3 | 23.3 21.3 25.5 27.1 | The EXAMPLE Example EXAMPLE Example |
Liquid accelerating chemicals composition is (part), and test number 14-10,14-11,14-13,14-14 share 10 parts raw material K, and test number 14-11-14-14 all share raw material O, and raw material O usage quantity is with R
2O converts and forms, for 100 parts SO
3(part).The pH of all liquid accelerating chemicalss is below 6.
Table 15
| Test number | Liquid accelerating chemicals | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 15-1 14-10 15-2 | 5 10 15 | 6.0 22.1 29.5 | EXAMPLE Example embodiment |
Liquid accelerating chemicals is for 100 parts of cement (part).
Table 16
| Test number | Calcium hydroxide | Aluminium hydroxide | Calcium sulfate | The anti-intrusion value of Pu Shi (N/mm 2) | Remarks |
| 16-1 16-2 16-3 16-4 | 0.5 0.8 3.0 5.0 | 0.0 0.0 0.0 0.0 | 0.0 0.0 0.0 0.0 | 15.7 17.1 24.1 25.1 | The EXAMPLE Example EXAMPLE Example |
| 16-5 16-6 16-7 16-8 | 0.0 0.0 0.0 0.0 | 0.5 0.8 3.0 5.0 | 0.0 0.0 0.0 0.0 | 16.2 19.4 26.8 27.8 | The EXAMPLE Example EXAMPLE Example |
| 16-9 | 3.0 | 3.0 | 0.0 | 28.5 | Embodiment |
| 16-10 16-11 16-12 16-13 | 3.0 3.0 3.0 3.0 | 3.0 3.0 3.0 3.0 | 1.0 1.5 5.0 7.0 | 29.2 30.1 32.5 31.6 | The EXAMPLE Example EXAMPLE Example |
Calcium hydroxide, aluminium hydroxide and calcium sulfate are all for 100 parts of cement (part).
Claims (16)
1. spray material is characterized in that, contains liquid accelerating chemicals, rapid hardening auxiliary agent and cement concrete and forms; Liquid accelerating chemicals contains aluminium source, sulphur source and fluorine source, wherein with respect to being converted into SO
3100 parts in sulphur source, with Al
2O
3Convert, the aluminium source of liquid accelerating chemicals is 25-110 part, and the fluorine source is 2-50 part as F, and the usage quantity of liquid accelerating chemicals is 5-15 part with respect to 100 parts of cement in the cement concrete; The rapid hardening auxiliary agent is selected from a kind of in calcium aluminate, calcium sulphoaluminate, ca aluminosilicate, calcium hydroxide and the aluminium hydroxide or more than two kinds, and the rapid hardening auxiliary agent is 0.05-25 part with respect to 100 parts of cement in the cement concrete.
2. spray material according to claim 1 is characterized in that liquid accelerating chemicals also contains alkanolamine.
3. spray material according to claim 2 is characterized in that, with respect to being converted into SO
3100 parts in sulphur source, alkanolamine is 1-30 part.
4. spray material according to claim 1 is characterized in that liquid accelerating chemicals also contains alkali metal source.
5. spray material according to claim 4 is characterized in that, with respect to being converted into SO
3100 parts in sulphur source, with R
2O converts, and alkali metal source is 2-50 part, and wherein R is a basic metal.
6. spray material according to claim 1 is characterized in that the pH of liquid accelerating chemicals is below 6.
7. spray material according to claim 1 is characterized in that, the Brian specific surface area value of rapid hardening auxiliary agent is at 2000cm
2More than/the g.
8. spray material according to claim 1 is characterized in that, the CaO in the calcium sulphoaluminate of rapid hardening auxiliary agent is 30-50 part, Al
2O
3Be 40-60 part, SO
3It is 5-20 part.
9. spray material according to claim 1 is characterized in that, the CaO in the ca aluminosilicate of rapid hardening auxiliary agent is 20-60 part, Al
2O
3Be 2-60 part, SiO
2It is 6-50 part.
10. spray material according to claim 1 is characterized in that, also contains calcium sulfate.
11. spray material according to claim 10 is characterized in that, with respect to 100 parts cement in the cement concrete, calcium sulfate is 1-7 part.
12. spray material according to claim 1 is characterized in that, also contains retardant.
13. spray material according to claim 12 is characterized in that, with respect to 100 parts cement in the cement concrete, retardant is 0.05-5 part.
14. spraying coating process is characterized in that, each spray material among the employing claim 1-13.
15. spraying coating process according to claim 14 is characterized in that, the calcium sulfate that adds liquid accelerating chemicals, rapid hardening auxiliary agent and add as required in the cement concrete that force feed comes sprays.
16. according to claim 14 or 15 described spraying coating process, it is characterized in that, with the rapid hardening auxiliary agent and the calcium sulfate and the cement concrete that add as required be pre-mixed, more liquid accelerating chemicals is added in the cement concrete of force feed, spray.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP295994/2003 | 2003-08-20 | ||
| JP296171/2003 | 2003-08-20 | ||
| JP296169/2003 | 2003-08-20 | ||
| JP2003295994 | 2003-08-20 | ||
| JP295995/2003 | 2003-08-20 | ||
| JP296170/2003 | 2003-08-20 |
Publications (2)
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|---|---|
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| CN100345792C true CN100345792C (en) | 2007-10-31 |
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ID=35476679
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200480001078XA Active CN100345792C (en) | 2003-08-20 | 2004-08-19 | Spraying material and spray technique employing the same |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008056716A1 (en) * | 2006-11-09 | 2008-05-15 | Denki Kagaku Kogyo Kabushiki Kaisha | Set accelerator and technique for spraying with the same |
| CN102173630B (en) * | 2011-01-04 | 2013-10-02 | 昆明合起工贸有限公司 | High-performance chlorine-free alkali-free liquid accelerating agent |
| CN107572856A (en) * | 2017-10-09 | 2018-01-12 | 常州琨瑶纺织品有限公司 | A kind of green alkali-free liquid concrete accelerator and preparation method thereof |
| CN112521047A (en) * | 2021-01-08 | 2021-03-19 | 成都楠裘榕科技有限公司 | Preparation method of concrete accelerator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047048A (en) * | 2000-05-25 | 2002-02-12 | Denki Kagaku Kogyo Kk | Liquid curing accelerator, rapid curing cement/concrete using the same and method of producing rapid curing cement/concrete |
| CN1407954A (en) * | 1999-12-08 | 2003-04-02 | Mbt控股有限公司 | Preparation of concrete accelerator |
-
2004
- 2004-08-19 CN CNB200480001078XA patent/CN100345792C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407954A (en) * | 1999-12-08 | 2003-04-02 | Mbt控股有限公司 | Preparation of concrete accelerator |
| JP2002047048A (en) * | 2000-05-25 | 2002-02-12 | Denki Kagaku Kogyo Kk | Liquid curing accelerator, rapid curing cement/concrete using the same and method of producing rapid curing cement/concrete |
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