CN101607833B - Reinforcing material of permeable hydraulic degraded unconsolidated rock and reinforcing method thereof - Google Patents
Reinforcing material of permeable hydraulic degraded unconsolidated rock and reinforcing method thereof Download PDFInfo
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Abstract
The invention discloses a reinforcing material of a permeable hydraulic unconsolidated rock. The reinforcing material comprises the following components: low carbon alcohol solution A with a phosphorus source substance as a main solute, wherein, a mineralized coupling agent is dissolved; polyhydroxy low carbon alcohol solution B with a calcium source substance as a main solute, wherein, a hardener and a dispersant are dissolved; and aqueous solution C with ammonium salt as a solute. Penetration operation is performed on the unconsolidated rock by natural flow, spraying, brush coating, soaking or applying methods. The alcohol solution A and the solution B can be mixed and permeated or sequentially permeated respectively, and then the aqueous solution C is permeated after permeation is finished. The reinforcing material has the advantages of easily available raw materials, mild preparation conditions, simple use method, good compatibility with the rock, acid corrosion resistance, obvious reinforcing effect, water soak resistance, no pollution and 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 receive 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 is an organic type of material mostly, and it is main network structure that these materials generate with the organic substance through crosslinking reaction, and certain fastening strength is arranged.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 is shown in 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 Win 40350 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 possibly 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 is improved, and makes 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 Win 40350 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: with phosphorus source material is master's low-carbon (LC) alcohols solution A, is main poly-hydroxy low-carbon (LC) alcohols solution B with the 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 title product calculates with the Win 40350, 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 Win 40350; The quality of stiffening agent is 3～5% of institute's reduced Win 40350 quality; The quality of dispersion agent is 2～3% of institute's reduced Win 40350 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 Win 40350 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 terepthaloyl moietie, USP Kosher or other poly-hydroxy low-carbon alcohol, can be independent/or mix and use, wherein be best with terepthaloyl moietie; 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, quicklime, calcium superoxide, calcium hydroxide etc., recommends to use quicklime.Phosphorus source material and calcium source substance are the main raw materials that forms Win 40350 series gelling material.Win 40350 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 quicklime in terepthaloyl moietie is merely about 1g/25ml, although more a lot of than in water, exceeding; 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, Hydrocerol A organism, recommends to use ACRYLIC EMULSION.The effect of dispersion agent is the current potential of asking that increases glued particulate through IX, 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, is fixed on calcium ion in the solution through sequestering action, 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 the preparing A alcoholic solution, and mineralising coupling agent of the present invention is a tetraethoxy; Hydroxy silicon oil; Siloxanes is like Union carbide A-162; Soft silica is like WHITE CARBON BLACK; Titanic acid ester is like 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 Win 40350 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 staple; After two kinds of solution are penetrated in the rock micropore; Entering along with the volatilization and the water in air of solvent are divided produces pectisation, and generating with silicon substituted hydroxy phosphatic rock is the inorganic glue adhesive material of staple; 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 accomplishing penetration operation at A, two kinds of alcohol solutions of B 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 following:
(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 the completion to be infiltrated, and wet water solution C again.It is before infiltration, A, two kinds of alcohol solutions of B to be mixed that process of osmosis is mixed by described elder generation again, after stirring, carries out penetration operation; Said process of osmosis successively is that ultra-sonic dispersion is 15～30 minutes before the infiltration with the every successively penetration operation of carrying out respectively at a distance from 15～60 minutes of B, two kinds of alcohol solutions of A.Again aqueous solution C was permeated several times at interval in 15～60 minutes after accomplishing penetration operation at A, two kinds of alcohol solutions of B.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 through the amount of adding alcoholic solvent, and aqueous solution C must permeate after accomplishing penetration operation at A, two kinds of alcohol solutions of B again.
The present invention preparation with the alcohols be solvent be the solution of staple with phosphorus and calcium; Solution along with the volatilization of solvent, adds the entering of moisture in the water and air after being penetrated in the rock micropore; Produce pectisation; Generation is the inorganic glue adhesive material of staple 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 the preparing 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, and preparation condition is gentle, and method of use is simple, and is good with the rock consistency, anti-acid etching, and 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 of 2-a (5000 times); The apatite layer (10000 times) on 2-b calcium carbonate granule surface
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 meliority 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 quicklime, is solvent with 25ml terepthaloyl moietie, is mixed with the B alcoholic solution through heating.Mix A, two kinds of solution of 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.Moving into
39.8mm * 80mm stainless steel hits in the real mould; Use 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 " the 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 property 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, under room temperature, be coated to the white marble marble surface, divide three times, whenever be coated with 1 time at a distance from 30 minutes.After leaving standstill 7 days, use quiet contact angle of JC2000A type/IT survey meter, the contact angle that records the blank stone appearance of being untreated is about (35 ± 5) °, and the stone appearance 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 appearance of protection processing and the hydrophilic-hydrophobic property of untreated blank stone appearance.Explain after protection is handled, kept its hydrophilic characteristic.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.ESEM (SEM) can be observed the surface down and form the orderly phosphatic rock microstructure resist 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 that sieves through 120 orders of this patent material and method protection in acidic bodies of water the electric situation of leading 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 is as shown in Figure 3, and 3-a is that immersion does not add the blank assay contrast that the calcium carbonate granule of protection is done, and 3-b soaks calcium carbonate granule behind the 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 is seen 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 quicklime (consumption is seen 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 table 1 a listed sequence mixing A, two kinds of solution of B, ultra-sonic dispersion is 15 minutes under the air tight condition.Mixing solutions all back carried out mixed reinforcement with calcium carbonate granule and powder and operates 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.Can know that by table 1 along with the increase of Vanadium Pentoxide in FLAKES and quicklime introducing amount, the ultimate compression strength and the surface hardness of reinforcing sample all increase thereupon.
Table 1 Vanadium Pentoxide in FLAKES and quicklime 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 |
| Quicklime (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 |
Embodiment 3
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 quicklime is a solvent with 25ml terepthaloyl moietie, is mixed with the B alcoholic solution through heating.Mix A, two kinds of solution of 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, can be known by 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 quicklime is a solvent with 25ml terepthaloyl moietie, is mixed with the B alcoholic solution through heating.Mix A, two kinds of solution of 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 in indoor open environment, placed 30 days.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 A, two kinds of solution of B; But mix with calcium carbonate granule and powder with the B alcoholic solution earlier, adding the A alcoholic solution afterwards again and carry out mixed reinforcement, the 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 silica 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.Explain that reinforcement means of the present invention also is suitable for siliceous loose rocks.
Embodiment 7
With embodiment 4, just with the mode of the 20ml mixing solutions for preparing, slowly infiltrate in the imitated sample of blank loose rocks that shaping and drying is good in advance with the dropping infiltration, obtain the penetration reinforcement sample.In indoor unlimited physical environment, place after 7 days, 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.Explain 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, be with 3 times of alcohol dilutions with 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, be with 5 times of alcohol dilutions with 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 ROHM emulsion, the result finds that mixing solutions has deposition to produce, and can not be used for penetration reinforcement.Explain that dispersion agent helps improving the stability that adds solid solution.
Embodiment 10
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 deposition in several hours.Explain 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.Can know that by 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, with the binding ability that influences presoma mixed solution and rock substrate; And the introducing amount is too much, and with influencing 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 being the preparing 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, just during the preparing 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 (quicklime); Also do not add other auxiliary agents, just in strengthening agent, add 0.5g ACRYLIC EMULSION (in 35ml ethanol and 25ml terepthaloyl moietie), 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 the preparing 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, explains 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 de-ionized is that solvent is mixed with the 200ml C aqueous solution, according to the technology of 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.Explanation is introduced the water-soluble fluid power of C and is played the effect of accelerating setting rate and raising ultimate compression strength in reinforcement process.
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.Explain that adopting immersion way, aqueous solution C also can play accelerates setting rate and the effect that improves ultimate compression strength.
Claims (7)
1. permeable hydraulic loose rocks reinforcement material, it is characterized in that described reinforcement material component comprises: with phosphorus source material is master's low-carbon (LC) alcohols solution A, and described low-carbon alcohol kind solvent A comprises: methyl alcohol, ethanol or propyl alcohol; With the calcium source substance is main poly-hydroxy low-carbon (LC) alcohols solution B, and described poly-hydroxy low-carbon alcohol kind solvent B comprises: terepthaloyl moietie or USP Kosher; 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 title product calculates with the Win 40350, 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 Win 40350; The quality of stiffening agent is 3～5% of institute's reduced Win 40350 quality; The quality of dispersion agent is 2～3% of institute's reduced Win 40350 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 Win 40350 quality, and described phosphorus source material is a Vanadium Pentoxide in FLAKES.
2. 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.
3. permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described calcium source substance comprises: quicklime or calcium hydroxide.
4. 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.
5. permeable hydraulic loose rocks reinforcement material according to claim 1 is characterized in that described stiffening agent is a silicofluoride, comprises calcium silicofluoride or zine fluosilicate.
6. 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 Hydrocerol A.
7. the said permeable hydraulic loose rocks of claim 1-6 reinforcement material is applied to the reinforcement means of rock, and its step is following:
(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 the completion to be infiltrated, and wet water solution C again; It is before infiltration, A, two kinds of alcohol solutions of B to be mixed that process of osmosis is mixed by described elder generation again, after stirring, carries out penetration operation; Said process of osmosis successively is that ultra-sonic dispersion is 15～30 minutes before the infiltration with the every successively penetration operation of carrying out respectively at a distance from 15～60 minutes of B, two kinds of alcohol solutions of A; Again many intervals of aqueous solution C were permeated in 15～60 minutes after accomplishing penetration operation at A, two kinds of alcohol solutions of B; 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 through the amount of adding alcoholic solvent, and aqueous solution C must permeate after accomplishing penetration operation at A, two kinds of alcohol solutions of B again.
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| CN103739307B (en) * | 2013-12-13 | 2015-08-05 | 四川大学 | A kind of sandstones stone cultural artifact protecting materials and methods for making and using same |
| CN104478478B (en) * | 2014-10-30 | 2016-05-11 | 杨富巍 | A kind of method for reinforcing and protecting of weathering sclerotin historical relic |
| CN104356827B (en) * | 2014-11-14 | 2017-05-31 | 华中师范大学 | A kind of nano stone surface conditioning agent and preparation method thereof |
| CN105254333B (en) * | 2015-09-30 | 2017-05-31 | 杨富巍 | A kind of stone cultural artifact method for reinforcing and protecting based on fluor-apatite material |
| CN105198487A (en) * | 2015-09-30 | 2015-12-30 | 杨富巍 | Surface protecting method for outdoor carbonate stone cultural relics and products |
| CN105272359A (en) * | 2015-09-30 | 2016-01-27 | 杨富巍 | Protection treatment method of calcium sulfate weathered layer on surface of limestone cultural relic |
| CN107022272B (en) * | 2016-02-02 | 2020-05-12 | 兰州城市学院 | Preparation method of novel permeable water-based floor coating |
| CN105733601B (en) * | 2016-02-03 | 2019-04-12 | 陕西师范大学 | A kind of earthen ruins consolidation against weathering agent and reinforcement means |
| CN106220238B (en) * | 2016-08-03 | 2017-10-20 | 洛阳理工学院 | The method of chemical protection that a kind of rock water resistant solution corrodes |
| CN107353016B (en) * | 2017-06-16 | 2020-11-03 | 浙江大学 | Preparation method of hydroxyapatite and application of hydroxyapatite in 3D printing and forming |
| CN108516869B (en) * | 2018-06-01 | 2019-02-22 | 沈小云 | The guard method of stone tablet class historical relic |
| CN111499408A (en) * | 2020-04-29 | 2020-08-07 | 同济大学 | Solidified compact carbonate material, solidification method and detection method thereof |
| CN115259409B (en) * | 2022-07-26 | 2023-11-17 | 上海净豚环保科技有限公司 | Calcification-preventing growth-promoting scale inhibitor for anaerobic granular sludge and preparation method thereof |
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| CN1884214A (en) * | 2006-06-21 | 2006-12-27 | 毛海燕 | Antiskid polished tiles |
| CN101010396A (en) * | 2004-09-01 | 2007-08-01 | 纳幕尔杜邦公司 | Anionic/cationic masonry sealing systems |
| CN101343191A (en) * | 2008-08-26 | 2009-01-14 | 浙江大学 | Permeation type hydraulic stone cultural relics reinforcing material and reinforcing method |
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| CN101010396A (en) * | 2004-09-01 | 2007-08-01 | 纳幕尔杜邦公司 | Anionic/cationic masonry sealing systems |
| CN1884214A (en) * | 2006-06-21 | 2006-12-27 | 毛海燕 | Antiskid polished tiles |
| CN101343191A (en) * | 2008-08-26 | 2009-01-14 | 浙江大学 | Permeation type hydraulic stone cultural relics reinforcing material and reinforcing method |
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