CN101607833A - The reinforcement material of permeable hydraulic degraded loose rocks and reinforcement means - Google Patents
The reinforcement material of permeable hydraulic degraded loose rocks and reinforcement means Download PDFInfo
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Abstract
A kind of permeable hydraulic loose rocks reinforcement material, described reinforcement material component comprises: with phosphorus source material is the low-carbon (LC) alcohols solution A of main solute, wherein dissolves in the mineralising coupling agent; With calcium source substance is the poly-hydroxy low-carbon (LC) alcohols solution B of main solute, wherein dissolves in stiffening agent and dispersion agent; And ammonium salt is the aqueous solution C of solute.Adopt nature trickling, spray, brushing, immersion or plaster application method that loose rocks is carried out penetration operation.Can A, B two kinds of alcohol solutions mix infiltration again or infiltration successively respectively earlier, after to be infiltrated the finishing, infiltration water solution C again.Reinforcement material raw material of the present invention is easy to get, the preparation condition gentleness, and using method is simple, and is good with the rock consistency, anti-acid etching, consolidation effect is obvious, soaking-resistant, environmental protection.
Description
Technical field
The invention belongs to stone material and stone cultural artifact protecting materials field, particularly a kind of reinforcement material and reinforcement means thereof of permeable hydraulic degraded loose rocks.
Background technology
China is with a long history, and numerous stone cultural artifacts and ancient building all are subjected to the threat of nature weathering, wherein much has been in Critical Condition, needs the protecting materials of excellent property badly and reinforces and protect.Surface layer protection material commonly used at present mostly is organic class material greatly, and these materials have certain fastening strength by the network structure of crosslinking reaction generation based on organic substance.But the shortcoming of organic materials also is significantly, mainly show as work-ing life short, weathering resistance is poor, good inadequately with the consistency of rock, some organism material also is easy to generate in wet environment and goes mouldy, and influences the outward appearance of historical relic.Comparatively speaking, indexs such as the weathering resistance of inorganic protecting materials and consistency all are better than organic materials.Before the 19th-century, inorganic materials just has been widely used in the surfacecti proteon of stone material, for example, and liming, the oxyhydroxide of barium or phosphoric acid salt etc.Because the crystallographic expansion of the contained salinity of solution, the use of some inorganic materials has aggravated the weathering of stone material on the contrary, causes correlative study to stagnate for a long time.The patent relevant with inorganic protecting materials that sees report at present is few.For the advantage of bringing into play inorganic protecting materials and overcome its defective, the novel inorganic protecting materials must solve following problem:
1, soluble salt problem, in the osmosis type water-based protective agent, inorganic materials is introduced with the form of salts solution often, therefore is difficult to avoid bringing into soluble salt, thereby causes that the salt crystalline destroys;
2, fastening strength problem, because the solvation of water, inorganic salt solution infiltrates after the rock micropore, separates out the powdery substance that is not cross-linked with each other often of formation, reinforcement effect is not strong;
3, permeability problems in order to reduce the harm of soluble salt, is often used indissoluble or slightly soluble inorganics, and the effective constituent that this conventional soln infiltrates seldom, therefore makes the paste shape more, influenced protectant perviousness thus.
In order to address the above problem, patent CN101343191 has proposed that a kind of what meet that the rock protection requires is the inorganic gel reinforcement material of the permeable hydraulic of solvent with alcohol.The new approaches of this patent be to use can more dissolving inorganics not with the alcoholic solution of soluble salt; Perviousness can; Solidify back gained hydroxyapatite and have fastening strength and weathering resistance preferably, with the consistency of geological diagnostics substrate.Making above-mentioned three problems obtain part thus solves.But this strengthening agent slant acidity may produce corrosive nature to the calcic rock thus, and preparation technology is also complicated simultaneously, and strengthening agent is longer set time.
Summary of the invention
The present invention is further developing of patent CN101343191, on the basis that keeps former method advantage, prescription and technology are improved, make the formulations prepared from solutions process be tending towards simple, the calcium contents of strengthening agent is obviously increased, stability is improved, and shorten dramatically set time, and is better with the bonding force of rock, the reinforcement material of preparation is neutral alkali partially, has avoided the danger of consequent corrosion calcic rock.
The present invention uses for reference sol-gel method, adopts high chemically reactive substance, preparation hydroxyapatite and make it to be used for the reinforcing and the protection of rock under normal temperature and pressure conditions.
Permeable hydraulic loose rocks reinforcement material provided by the invention, described reinforcement material component comprises: based on the low-carbon (LC) alcohols solution A of phosphorus source material, based on the poly-hydroxy low-carbon (LC) alcohols solution B of calcium source substance, and the aqueous solution C that has dissolved ammonium salt.Wherein can dissolve in the mineralising coupling agent among the alcohol solution A; Can dissolve in stiffening agent and dispersion agent among the alcohol solution B.The consumption of described A, two kinds of alcoholic solutions of B all is that target product calculates with the hydroxyapatite, and the mol ratio of control phosphorus and calcium is: phosphorus: calcium=1: 1.65～1: 1.85; The quality of mineralising coupling agent is 6～9% of institute's reduced hydroxyapatite; The quality of stiffening agent is 3～5% of institute's reduced hydroxyapatite quality; The quality of dispersion agent is 2～3% of institute's reduced hydroxyapatite quality.Described aqueous solution C is that ammonium salt concentration is the dilute aqueous soln of 0.001～0.1mol/L, and consumption is 0.2～5% of institute's reduced hydroxyapatite quality.
Low-carbon alcohol kind solvent of the present invention is methyl alcohol, ethanol, propyl alcohol or other low-carbon alcohol, can be independent/or mix and use, wherein be best with ethanol; Described poly-hydroxy low-carbon alcohol kind solvent is ethylene glycol, glycerol or other poly-hydroxy low-carbon alcohol, can be independent/or mix and use, wherein be best with ethylene glycol; Described ammonium salt is ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium oxalate, volatile salt, bicarbonate of ammonia etc.
Phosphorus of the present invention source material is Vanadium Pentoxide in FLAKES, triethyl phosphate, phosphoric acid, peroxophosphoric acid, tetra-sodium or Tripyrophosphoric acid etc., recommends to use Vanadium Pentoxide in FLAKES; Calcium source substance of the present invention is calcium metal, calcium oxide, calcium peroxide, calcium hydroxide etc., recommends to use calcium oxide.Phosphorus source material and calcium source substance are the main raw materials that forms hydroxyapatite series gelling material.Hydroxyapatite series gel is one of most important inorganic adhesive, excellent property, and mixing property and plasticity-are good, and moulding process is easy.At present, existing many application the aspect medical science.Insufficiently be, generally all exist that viscosity is very big, poor permeability with the body of paste form.In order to reach the purpose that rock permeability is reinforced, the present invention specially is designed to the form of alcohols liquid solution and uses.
The reinforcing of deterioration rock depends on that can reinforcement material form successive thing phase in the rock micropore, thereby bonding loose microparticle and microfissure reach the purpose of reinforcing.Thus, the introducing amount of effective ingredient is an important factors.Experiment shows that phosphorus of the present invention source material just can be mixed with the A alcoholic solution in physical environment; And need heat and could dissolve during calcium source substance of the present invention preparation B alcoholic solution, and the dissolved amount is limited, and for example the solubleness of calcium oxide in ethylene glycol only is about 1g/25ml, although more a lot of than exceeding in water, but reach the ideal consolidation effect, this concentration still is on the low side.For this reason, the present invention has introduced a spot of stiffening agent and dispersion agent when preparation B alcoholic solution, and to promote the solubleness of calcium source substance in poly-hydroxy low-carbon alcohol kind solvent, this is the key that improves fastening strength.
The stiffening agent that the present invention uses is silicofluoride, comprises calcium silicofluoride, calcium Magnesium Silicate q-agent or zine fluosilicate etc., and they have preservative activity concurrently.The dispersion agent that the present invention uses is many carboxyls such as ACRYLIC EMULSION, citric acid organism, recommends to use ACRYLIC EMULSION.The effect of dispersion agent is the current potential of asking that increases glued particulate by ion-exchange, makes repulsion increase between micelle, and mobile the enhancing avoided generating flucculation structure between micelle simultaneously, helps the bonding force of weighting agent and substrate.In addition, dispersion agent can effectively suppress the premature hardening of reinforcement material, by sequestering action calcium ion is fixed in the solution, suppresses the sedimentary formation of calcium phosphate.Certainly consumption is seldom.
In order to improve the consistency of strengthening agent and rock substrate, the present invention has used the mineralising coupling agent when preparation A alcoholic solution, and mineralising coupling agent of the present invention is a tetraethoxy; Hydroxy silicon oil; Siloxanes is as Union carbide A-162; Soft silica is as white carbon black; Titanic acid ester is as tetrabutyl titanate; Aluminic acid ester and boron aluminic acid ester etc.These materials all have reinforced effects preferably.The effect of mineralising coupling agent is to be mixed in the reticulated structure of reaction formation, and hydroxyapatite is linked to each other with the rock substrate, to improve cohesive strength.
Basic ideas of the present invention are that preparing with phosphorus and calcium respectively is the alcohol solution of main component, after two kinds of solution are penetrated in the rock micropore, along with the volatilization of solvent and entering of water in air branch, produce pectisation, generation is the inorganic glue adhesive material of main component with silicon substituted hydroxy phosphatic rock, thereby bonding connects the microparticle and the microfissure of cracking rock, reaches the purpose of reinforcing loose stone cultural artifact in imminent danger.In the forming process of above-mentioned hydraulicity gel, moisture content is one of important participation component, and the present invention has specially introduced aqueous solution C for the process of the whole reinforcing process of control.In order to make strengthening agent fully after the infiltration pectisation take place again, aqueous solution C must permeate after two kinds of alcohol solutions of A, B are finished penetration operation again, aqueous solution C can accelerate the solidification process of reinforcement material, to driving away residual alcoholic solvent certain promotion is arranged simultaneously.
Permeable hydraulic reinforcement material of the present invention is applied to the reinforcement means of deterioration loose rocks, and its step is as follows:
(1) solution allocation: solution comprises: be the low-carbon (LC) alcohols solution A of main solute with phosphorus source material 1., wherein can dissolve in the mineralising coupling agent; 2. be the poly-hydroxy low-carbon (LC) alcohols solution B of main solute with calcium source substance, wherein can dissolve in stiffening agent and dispersion agent; 3. with the ammonium salt aqueous solution C of solute.
(2) penetration operation: adopt nature trickling, spray, brushing, immersion or plaster application method that loose rocks is carried out penetration operation.Penetration operation is divided into two kinds of alcohol solutions of A, B and mixes infiltration again or infiltration successively respectively earlier, after to be infiltrated the finishing, and infiltration water solution C again.It is before infiltration two kinds of alcohol solutions of A, B to be mixed that process of osmosis is mixed by described elder generation again, after stirring, carries out penetration operation; Described process of osmosis successively is that two kinds of alcohol solutions of B, A were carried out penetration operation successively respectively every 15～60 minutes, and ultra-sonic dispersion is 15～30 minutes before the infiltration.After finishing penetration operation, two kinds of alcohol solutions of A, B again aqueous solution C was permeated several times at interval in 15～60 minutes.The usage quantity of A, two kinds of alcohol solutions of B need be carried out the proportioning adjustment as the case may be, the key of proportioning is the ratio of control phosphorus, calcium, the viscosity of solution can be regulated by the amount of adding alcoholic solvent, and aqueous solution C must permeate after two kinds of alcohol solutions of A, B are finished penetration operation again.
The present invention preparation with the alcohols be solvent be the solution of main component with phosphorus and calcium, after solution is penetrated in the rock micropore, volatilization along with solvent, add entering of moisture in the water and air, produce pectisation, generation is the inorganic glue adhesive material of main component with silicon substituted hydroxy phosphatic rock, thereby bonding connects the microparticle and the microfissure of cracking rock, reaches the purpose of reinforcing loose rocks.The present invention has introduced a spot of stiffening agent and dispersion agent in order to promote the solubleness of calcium source substance in poly-hydroxy low-carbon alcohol kind solvent when preparation B alcoholic solution; The present invention has used the mineralising coupling agent in order to improve the consistency of strengthening agent and rock substrate when preparation A alcoholic solution; The present invention has specially introduced aqueous solution C in order to accelerate the process of setting of strengthening agent.Reinforcement material raw material of the present invention is easy to get, the preparation condition gentleness, and using method is simple, and is good with the rock consistency, anti-acid etching, consolidation effect is obvious, soaking-resistant, environmental protection.
The present invention compares with patent CN101343191, and tangible improvement is arranged:
1, the calcium contents of strengthening agent obviously improves, and effective reinforcing composition of infiltration is increased;
2, the bonding force of strengthening agent and rock substrate is better, and fastening strength improves;
3, the stability of strengthening agent self is better, is more convenient for storing and transportation;
4, strengthening agent itself is neutral alkali partially, has avoided the danger of consequent corrosion calcic rock;
5, make the preparation technology of strengthening agent simpler;
6, shortened dramatically the set time of strengthening agent.
Description of drawings
Fig. 1 is to the contact angle detection photo of water
The blank white marble marble surface of 1-a; White marble marble surface after 1-b protects with the inventive method;
Fig. 2 calcium carbonate granule surface forms the SEM photo before and after the phosphatic rock mineralising crystallizing layer
The blank calcium carbonate granule surface (5000 times) of 2-a; The apatite layer on 2-b calcium carbonate granule surface (10000 times)
Fig. 3 pH be in the acidic aqueous solution of 3-4 specific conductivity over time
3-a soaks the calcium carbonate granule that does not add protection; 3-b soaks the calcium carbonate granule behind the reinforcement protection;
Embodiment
In order to set forth implementation method of the present invention and superiority in more detail, further the present invention is elaborated below in conjunction with experimental result.
1. solution allocation: taking by weighing the 0.47g Vanadium Pentoxide in FLAKES, is solvent with 35ml ethanol, adds 1.5ml tetraethoxy mineralising coupling agent again, is mixed with the A alcoholic solution; Getting the 4.80g calcium oxide, is solvent with 25ml ethylene glycol, is mixed with the B alcoholic solution through heating.Mix two kinds of solution of A, B, ultra-sonic dispersion is 15 minutes under the air tight condition.Mixing solutions used in 1 hour.
2. fastening strength detects: accurately take by weighing 80g particulate calcium carbonate (100 orders sieve) and 80g whiting (1000 orders sieve), after mixing, add 20ml water, continue thorough mixing.Move into
39.8mm * 80mm stainless steel hits in the real mould, uses the 566g compaction hammer, height 277mm hits real 50 times, and sample is positioned over seasoning in the indoor open environment after the demoulding.The loose rocks that obtains being shaped is copied sample.The same operation changes 20ml water into mixing solutions that 20ml disposes, obtains the mixed reinforcement sample.Carrying out ultimate compression strength with the pressure tester then measures.Instrument and method all design with reference to " People's Republic of China's geotechnical test method national standard ".Naturally placing the mean compressive strength that records blank imitated sample after 14 days is 51.4N, and the mean compressive strength of mixed reinforcement sample is 489.1N, reinforces back ultimate compression strength and has improved 8.5 times nearly.
3. anti-immersion detection: the mixed reinforcement sample soaks 10 days in water after, and compare the no obvious visible variation in surface before the water logging bubble.In air after the seasoning, weighing, with soak before compare, mass change is less than 5%.And blank imitated sample, in case with after water contacts, disintegration immediately.
4. hydrophobic nature detects: get the mixing solutions of 3ml configuration, be coated to the white marble marble surface under room temperature, divide three times, be coated with 1 time every 30 minutes.After leaving standstill 7 days, use quiet contact angle of JC2000A type/interfacial tension survey meter, the contact angle that records the blank stone sample that is untreated is about (35 ± 5) °, and the stone sample contact angle that protection was handled slightly increases, and is in (40 ± 5) °.The take off data of contact angle shows do not have considerable change through the stone sample of protection processing and the hydrophilic-hydrophobic of untreated blank stone sample.Explanation has been kept its hydrophilic characteristic after protection is handled.Can avoid the inconsistent problem of newborn interface on rerum natura like this.Referring to the contact angle detection photo Fig. 1 to water, 1-a is blank white marble marble surface; 1-b is with the white marble marble surface after the inventive method protection.
5. microscopic examination and analysis: get the mixing solutions 30ml that is disposed, be statically placed in the system of opening wide, put into the calcite nuggets of 1.0mm * 7.5mm * 7.5mm, take out dry after 15 days.Scanning electron microscope (SEM) can be observed the surface down and form the orderly phosphatic rock microstructure protective layer of compact structure, referring to Fig. 2.2-a is blank calcium carbonate granule surface (amplifying 5000 times); Fig. 2-b is the apatite layer (amplifying 10000 times) that the calcium carbonate granule surface forms.
6. the white marble particle electricity in acidic bodies of water that sieves through 120 orders of this patent material and method protection is led the situation of variation referring to Fig. 3.Operating process is for to place deionized water with above-mentioned particle; the hydrochloric acid that evenly and lentamente adds pH=3 ≈ 4; the result as shown in Figure 3; 3-a is that immersion does not add the blank assay contrast that the calcium carbonate granule of protection is done; calcium carbonate granule behind the 3-b immersion reinforcement protection; As time goes on the specific conductivity of its solution increases earlier, remains unchanged then.The calcium carbonate granule of results of comparison explanation behind this patent strengthening agent reinforcement protection has good acid resistance.
Method changes the amount of dissolving in of solution formula and phosphorus and calcium with embodiment 1.
Solution preparation: take by weighing an amount of Vanadium Pentoxide in FLAKES (consumption sees Table 1), add the 35ml alcohol solvent respectively, add 1.5ml tetraethoxy mineralising coupling agent again, be mixed with the series A alcoholic solution; Take by weighing an amount of calcium oxide (consumption sees Table 1) successively, take by weighing 0.35g ACRYLIC EMULSION dispersion agent more respectively, 0.45g magnesium silicofluoride stiffening agent adds the 25ml ethylene glycol solvent, is mixed with serial B alcoholic solution through heating.Press the listed order of table 1 and mix two kinds of solution of A, B, ultra-sonic dispersion is 15 minutes under the air tight condition.Mixing solutions all back carried out mixed reinforcement operation with calcium carbonate granule and powder in 30 minutes, the unification of gained sample was positioned in the indoor open environment 30 days, carried out the detection of ultimate compression strength and surface hardness then, and the gained data are also listed in the table 1.As shown in Table 1, along with the increase of Vanadium Pentoxide in FLAKES and calcium oxide introducing amount, the ultimate compression strength and the surface hardness of reinforcing sample all increase thereupon.
Table 1 Vanadium Pentoxide in FLAKES and calcium oxide introducing amount are to the influence of reinforcement performance
| Vanadium Pentoxide in FLAKES (g) | ??0.44 | ??0.65 | ??1.17 | ??2.38 | ??3.3 | ??3.4 | ??4.05 |
| Calcium oxide (g) | ??0.56 | ??0.9 | ??1.5 | ??3.0 | ??4.07 | ??4.25 | ??4.8 |
| Be reinforced the ultimate compression strength (N) of sample | ??271.3 | ??344.9 | ??517.5 | ??604.4 | ??789.5 | ??854.9 | ??1034.7 |
| Be reinforced the surface hardness (A) of sample | ??17.1 | ??25.9 | ??31.3 | ??34.5 | ??40.2 | ??51.3 | ??60.8 |
With embodiment 2, just change the storage period of sample.
The solution preparation: taking by weighing the 2.38g Vanadium Pentoxide in FLAKES, is solvent with 35ml ethanol, adds the 1.5ml tetraethoxy again and is mixed with the A alcoholic solution; Take by weighing the 0.35g ACRYLIC EMULSION successively, the 0.45g magnesium silicofluoride, the 3.0g calcium oxide is a solvent with 25ml ethylene glycol, is mixed with the B alcoholic solution through heating.Mix two kinds of solution of A, B, ultra-sonic dispersion is 15 minutes under the air tight condition.Mixing solutions carried out the mixed reinforcement operation with calcium carbonate granule and powder in 30 minutes, the gained sample is placed certain fate (seeing Table 2) successively in indoor open environment, carry out the detection of ultimate compression strength and surface hardness then, the gained data are also listed in the table 2, as shown in Table 2, along with the increase of storage period, the ultimate compression strength and the surface hardness of reinforcing sample all increase thereupon.
Table 2 storage period is to the influence of sample reinforcement performance
| Be reinforced the time that sample places (my god) | ??10 | ??20 | ??30 | ??50 |
| Be reinforced the ultimate compression strength (N) of sample | ??380.1 | ??558.2 | ??604.4 | ??759.5 |
| Be reinforced the surface hardness (A) of sample | ??20.8 | ??25.3 | ??34.5 | ??47.2 |
Embodiment 4
With embodiment 3, take by weighing the 3.37g Vanadium Pentoxide in FLAKES, be solvent with 35ml ethanol, add the 1.5ml tetraethoxy again and be mixed with the A alcoholic solution; Take by weighing the 0.35g ACRYLIC EMULSION successively, the 0.45g magnesium silicofluoride, the 4.2g calcium oxide is a solvent with 25ml ethylene glycol, is mixed with the B alcoholic solution through heating.Mix two kinds of solution of A, B, ultra-sonic dispersion is 15 minutes under the air tight condition.Mixing solutions mixed with calcium carbonate granule and powder in 30 minutes, and hit real moulding on request in the immigration stainless steel mould, and gained is reinforced sample and placed 30 days in indoor open environment.The ultimate compression strength that obtains reinforcing sample is 744.4N, and surface hardness is 51.3A.
Embodiment 5
With embodiment 4, just do not mix two kinds of solution of A, B, but mix with calcium carbonate granule and powder with the B alcoholic solution earlier, add the A alcoholic solution afterwards again and carry out mixed reinforcement, sample after the moulding was placed 30 days in indoor open environment, the ultimate compression strength that gained is reinforced sample is 729.2N, and surface hardness is 51.2A.Mix use no matter strengthening agent is described, still separately use, can both obtain consolidation effect preferably.
Embodiment 6
With embodiment 4, just change calcium carbonate granule and powder into quartz sand and powder, its constant rate.The ultimate compression strength that gained is reinforced sample is close with embodiment 4, and surface hardness is slightly larger than embodiment 4.Illustrate that reinforcement means of the present invention also is suitable for siliceous loose rocks.
Embodiment 7
With embodiment 4, just the mode that the 20ml mixing solutions for preparing is permeated with dropping is slowly infiltrated in the imitated sample of blank loose rocks that shaping and drying is good in advance, obtains the penetration reinforcement sample.Place after 7 days in indoor unlimited physical environment, the penetration reinforcement sample improves about 8 times than the ultimate compression strength of blank sample, the not disintegration more than 15 days of water logging bubble.Section detects the depth of penetration of finding mixing solutions and is about about 2/3 of pure water depth of penetration.Illustrate that the present invention can be used for the penetration reinforcement of deterioration rock.
Embodiment 8
With embodiment 7, just mixing solutions is added ethanol, dilute by 1: 1 volume ratio, the viscosity of penetration reinforcement solution is reduced.And then carry out penetration reinforcement with the mode that drips infiltration, and gained penetration reinforcement sample was placed in indoor open environment after 7 days, and the penetration reinforcement sample improves about 8 times than the ultimate compression strength of blank sample, and not disintegration more than 75 days is steeped in water logging.
With above-mentioned method, just with 3 times of alcohol dilutions of mixing solutions.Gained penetration reinforcement sample improves about 7 times than the ultimate compression strength of blank sample.Can stand the water logging bubble more than 75 days.
With above-mentioned method, just with 5 times of alcohol dilutions of mixing solutions.Gained penetration reinforcement sample improves about 5 times than the ultimate compression strength of blank sample.Can stand the water logging bubble more than 30 days.
More than in the experiment, the viscosity ratio embodiment 7 of strengthening agent progressively reduces, and perviousness progressively increases, and section detects discovery can be near the depth of penetration of pure water with the depth of penetration of mixing solutions behind the alcohol dilution.Explanation is reaching under the prerequisite of certain fastening strength, and the method that the present invention can adopt alcoholic solvent that former strengthening agent is diluted improves the depth of penetration of strengthening agent to rock.
Embodiment 9
With embodiment 4, when just preparing the B alcoholic solution, do not add dispersion agent polyacrylic acid emulsion, found that mixing solutions has precipitation to produce, and can not be used for penetration reinforcement.Illustrate that dispersion agent helps improving the stability that adds solid solution.
With embodiment 4, when just preparing the B alcoholic solution, the consumption of dispersion agent ACRYLIC EMULSION is increased to 0.5g, the stability of gained mixing solutions and embodiment 1 are similar as a result, promptly can both keep solution and not produce precipitation in several hours.Illustrate that too much dispersion agent there is no need.
Embodiment 11
With embodiment 4, just in mixed solution, add the tetraethoxy (seeing Table 3) of different amounts respectively respectively, the corresponding ultimate compression strength of gained mixed reinforcement sample is also listed in the table 3.As shown in Table 3, the introducing amount of tetraethoxy has optimum value to reinforcement performance, roughly near 1.5mL.Analyze reason, tetraethoxy introducing amount is very few, will influence the binding ability of presoma mixed solution and rock substrate; And the introducing amount is too much, will influence the dispersiveness of presoma mixed solution in the rock micropore, because tetraethoxy is compared with rock, both polarity differences are bigger.
Table 3 tetraethoxy introducing amount is to the influence of sample fastening strength
Embodiment 12
With embodiment 4, when just preparing the A alcoholic solution, it is nano-scale white carbon black that the mineralizer tetraethoxy is changed, and the ultimate compression strength of gained mixed reinforcement sample is close with embodiment 4 as a result.
With above-mentioned method, when just preparing the A alcoholic solution, the consumption of mineralizer white carbon black is increased to 0.5g, the ultimate compression strength of the compressive strength rate The above results of gained mixed reinforcement sample descends to some extent as a result.
The above results is made carbon black clear also has optimum value as its consumption of mineralizer.
Embodiment 13
With embodiment 4, just in prescription, do not add phosphorus source (Vanadium Pentoxide in FLAKES) and calcium source (calcium oxide), also do not add other auxiliary agents, just add 0.5g ACRYLIC EMULSION (in 35ml ethanol and 25ml ethylene glycol) in strengthening agent, the ultimate compression strength of gained mixed reinforcement sample is 184.2N;
The same, just with magnesium silicofluoride instead of propylene yogurt liquid, the ultimate compression strength of gained mixed reinforcement sample is 132.1N.
Clearly The above results is far away from embodiment 4, and the generation of calcium phosphate is mainly given the credit in the raising of sample fastening strength among this explanation the present invention.
Embodiment 14
With embodiment 4, just when preparation A alcoholic solution, mineralising coupling agent tetraethoxy is replaced with butyl (tetra) titanate, and the ultimate compression strength of gained mixed reinforcement sample is close with the ultimate compression strength of embodiment 4, illustrates that mineralising coupling agent butyl (tetra) titanate also can play good mineralizer action of coupling agents.
Embodiment 15
With embodiment 4, just take by weighing the 20g Secondary ammonium phosphate in addition again, with the deionization is that solvent is mixed with the 200ml C aqueous solution, technology according to embodiment 4, when sample from stainless steel mould, take out place 1 hour after, divide three minor ticks 15～30 minutes, and dripped the C aqueous solution that amounts to 20ml at sample surfaces.The hardness of the mixed reinforcement sample of gained just improves a lot at short notice as a result, and the ultimate compression strength that records also is significantly improved, and reaches 823.5N.The C aqueous solution is introduced in explanation in reinforcement process can play the effect of accelerating setting rate and improving ultimate compression strength.
Embodiment 16
With embodiment 15, just will place sample after 1 hour and divide and be soaked in for three times among the aqueous solution C, soaked soak time 2 hours at interval 5 minutes at every turn.The hardness and the ultimate compression strength of the mixed reinforcement sample of gained also all are greatly improved at short notice as a result, and the ultimate compression strength that records is a little more than embodiment 15.Illustrate and adopt immersion way, aqueous solution C also can play the effect of accelerating setting rate and improving ultimate compression strength.
Claims (10)
1, a kind of permeable hydraulic loose rocks reinforcement material, it is characterized in that described reinforcement material component comprises: based on the low-carbon (LC) alcohols solution A of phosphorus source material, poly-hydroxy low-carbon (LC) alcohols solution B based on calcium source substance, and the aqueous solution C that has dissolved ammonium salt, wherein dissolve in the mineralising coupling agent among the alcohol solution A; Dissolve in stiffening agent and dispersion agent among the alcohol solution B; The consumption of described A, two kinds of alcoholic solutions of B all is that target product calculates with the hydroxyapatite, and the mol ratio of control phosphorus and calcium is: phosphorus: calcium=1: 1.65～1: 1.85; The quality of mineralising coupling agent is 6～9% of institute's reduced hydroxyapatite; The quality of stiffening agent is 3～5% of institute's reduced hydroxyapatite quality; The quality of dispersion agent is 2～3% of institute's reduced hydroxyapatite quality; Described aqueous solution C is that ammonium salt concentration is the dilute aqueous soln of 0.001～0.1mol/L, and consumption is 0.2～5% of institute's reduced hydroxyapatite quality.
2, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described low-carbon alcohol kind solvent comprises: methyl alcohol, ethanol or propyl alcohol.
3, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described poly-hydroxy low-carbon alcohol kind solvent comprises: ethylene glycol or glycerol.
4, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described ammonium salt comprises: ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium oxalate, volatile salt or bicarbonate of ammonia.
5, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described phosphorus source material comprises: Vanadium Pentoxide in FLAKES, triethyl phosphate, phosphoric acid, peroxophosphoric acid, tetra-sodium or Tripyrophosphoric acid.
6, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described calcium source substance comprises: calcium oxide, magnesium oxide, zinc oxide, calcium hydroxide or magnesium hydroxide.
7, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described mineralising coupling agent comprises: tetraethoxy, hydroxy silicon oil, siloxanes, white carbon black or titanic acid ester.
8, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described stiffening agent is a silicofluoride, comprises calcium silicofluoride, calcium Magnesium Silicate q-agent or zine fluosilicate.
9, permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described dispersion agent is many carboxyls organism, comprises vinylformic acid or citric acid.
10, the described permeable hydraulic loose rocks of claim 1-9 reinforcement material is applied to the reinforcement means of rock, and its step is as follows:
(1) solution allocation: solution comprises: be the low-carbon (LC) alcohols solution A of main solute with phosphorus source material 1., wherein dissolve in the mineralising coupling agent; 2. be the poly-hydroxy low-carbon (LC) alcohols solution B of main solute with calcium source substance, wherein dissolve in stiffening agent and dispersion agent; 3. with the ammonium salt aqueous solution C of solute;
(2) penetration operation: adopt nature trickling, spray, brushing, immersion or plaster application method that loose rocks is carried out penetration operation; Penetration operation is divided into two kinds of alcohol solutions of A, B and mixes infiltration again or infiltration successively respectively earlier, after to be infiltrated the finishing, and infiltration water solution C again; It is before infiltration two kinds of alcohol solutions of A, B to be mixed that process of osmosis is mixed by described elder generation again, after stirring, carries out penetration operation; Described process of osmosis successively is that two kinds of alcohol solutions of B, A were carried out penetration operation successively respectively every 15～60 minutes, and ultra-sonic dispersion is 15～30 minutes before the infiltration; After finishing penetration operation, two kinds of alcohol solutions of A, B more intervals of aqueous solution C were permeated in 15～60 minutes; The usage quantity of A, two kinds of alcohol solutions of B need be carried out the proportioning adjustment as the case may be, the key of proportioning is the ratio of control phosphorus, calcium, the viscosity of solution can be regulated by the amount of adding alcoholic solvent, and aqueous solution C must permeate after two kinds of alcohol solutions of A, B are finished penetration operation again.
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