CN101139215A - Calcium carbonate biomineralization reinforcing method for calcium carbonate type stone cultural relics - Google Patents
Calcium carbonate biomineralization reinforcing method for calcium carbonate type stone cultural relics Download PDFInfo
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- CN101139215A CN101139215A CNA2007100704207A CN200710070420A CN101139215A CN 101139215 A CN101139215 A CN 101139215A CN A2007100704207 A CNA2007100704207 A CN A2007100704207A CN 200710070420 A CN200710070420 A CN 200710070420A CN 101139215 A CN101139215 A CN 101139215A
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- lime carbonate
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- biomineralization
- calcium
- stone cultural
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 239000004575 stone Substances 0.000 title claims abstract description 35
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000033558 biomineral tissue development Effects 0.000 title claims description 42
- 230000003014 reinforcing effect Effects 0.000 title claims description 23
- 239000000463 material Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 92
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 65
- 239000011435 rock Substances 0.000 claims description 40
- 238000009415 formwork Methods 0.000 claims description 33
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 28
- 239000000920 calcium hydroxide Substances 0.000 claims description 28
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 28
- 230000002787 reinforcement Effects 0.000 claims description 20
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 229920000945 Amylopectin Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- -1 amphiphile function compound Chemical class 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 102000008186 Collagen Human genes 0.000 claims description 8
- 108010035532 Collagen Proteins 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001287 Chondroitin sulfate Polymers 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229940059329 chondroitin sulfate Drugs 0.000 claims description 6
- 230000003204 osmotic effect Effects 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920002683 Glycosaminoglycan Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012047 saturated solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 241000272522 Anas Species 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 102000002322 Egg Proteins Human genes 0.000 claims description 2
- 108010000912 Egg Proteins Proteins 0.000 claims description 2
- 239000001828 Gelatine Substances 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 210000004681 ovum Anatomy 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000003876 biosurfactant Substances 0.000 claims 2
- 229920001436 collagen Polymers 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 2
- 238000010790 dilution Methods 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 6
- 238000007906 compression Methods 0.000 abstract description 6
- 230000006835 compression Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000001089 mineralizing effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 22
- 239000004579 marble Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical group CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000167854 Bourreria succulenta Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000010010 raising Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
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- 239000010433 feldspar Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention discloses a calcium carbonate biological mineralizing and strengthening method for calcium carbonate stone cultural relic. The technical process of the present invention is that: the solvent is first used for cleaning the surface of the stone cultural relic; and then the present invention uses a compound solution with biological amphipathic function as a organic molding board to pretreat the surface of the stone cultural relic and to make the surface of the stone add with a functional group unit; the supersaturation solution of calcium carbonate is used for making with infiltration treatment; under the control of the functional group unit, the calcium carbonate is inducted to grow into core directional crystal; the rocked and incompact grain can be connected so as to make the strengthened protection for the surface of the stone material. The present invention has the advantages of similar property between the protective material and the base material, much better compatibility; the present invention does not change the appearance, color and hand feeling of the protected stone cultural relic; and the compression strength, water resistance, acidity resistance and soiling resistance are improved and enhanced greatly.
Description
Technical field
The present invention relates to the lime carbonate biomineralization reinforcing method of loose rocks, the top layer that is mainly used in lime carbonate class stone cultural artifact in imminent danger reinforces.
Background technology
A large amount of stone cultural artifacts that remnants in thousands of years is got off are important records of Chinese nation's civilized history, are valuable historical data in kind and tourist resources.Sleet hardships all the year round makes rock surface deterioration gradually, The modern industry is polluted and acid rain has quickened the speed of erosion damage especially, the surface structure of some rocks is very loose, even be in and touch the loose condition (of surface) that promptly powders away, press for and take necessary top layer consolidation process, to prolong the life-span of historical relic.But, also do not have gratifying top layer reinforcement material at present.Inorganic reinforcing material once was extensive use of before 19th-century, mainly comprised liming, the oxyhydroxide of barium or phosphoric acid salt etc., use found that, inorganic reinforcing material tends to form crust layer on the stone cultural artifact surface, not only changes color and outward appearance, also peels off easily.In recent decades, organic polymer is a most widely used stone cultural artifact top layer reinforcement material, for example, and Resins, epoxy, acrylic resin, especially organosilicon and organic fluorine base polymer etc.Although organic polymer has many advantages, the long-range effect of reinforcing is still unsatisfactory.Since organic polymer material actual useful life in the open air generally only several years, maximum two, 30 years.Macromolecular material after the inefficacy causes in various degree influence can for historical relic itself and follow-up reinforcing, for example yellowing, generation patch, blocking microporous and efflorescence etc.
Practice shows that ideal stone cultural artifact protecting materials at first should be good with rock body consistency.The control of consistency mainly contains two aspects, and the one, the microtexture of protecting materials should be regulated according to the situation of substrate, and the 2nd, the attribute of material should be close with basement rock as far as possible, preferably with a kind of material.At present, the material about stone material and stone cultural artifact protection in the Chinese patent all is organic class basically, as the patent No. 89103208.8 and application number 200410043975.9 etc.Several years ago, the long and good characteristics of rock consistency according to the natural caoxalate biomineralization thing life-span of finding, the inventor has proposed the new stone cultural artifact surface protecting material of a class, i.e. biomineralization material.The great advantage of biomineralization material is to select for use different organic formworks to come the microtexture of controlled material, for example, the caoxalate surfacecti proteon material that is used for calcic stone material and stone cultural artifact that in China Patent No. 00119382.1, proposes, and the calcium phosphate biomineralization reinforcing method that in Chinese application number 200710066859.2, proposes.China's lime carbonate rocks is widely distributed; with the lime carbonate rocks is the stone cultural artifact One's name is legion of substrate; though the material properties and the lime carbonate of caoxalate and calcium phosphate are close, not lime carbonate after all, the present invention can remedy the reinforcement protecting material defective different with the base material attribute.
Summary of the invention
It is identical with the base material attribute to the purpose of this invention is to provide a kind of protecting materials, the biomineralization reinforcing method of the sour calcium class stone cultural artifact that consistency is good.
The lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact of the present invention, the biomineralization thing material of the lime carbonate of usefulness controlled architecture, the stone cultural artifact of reinforcement protection lime carbonate class.
The present invention takes following measures in order to achieve the above object:
It is clean at first will to wait to reinforce the surface cleaning of rock with cleaning solvent; The organic formwork solution-treated rock surface that is mixed with biological amphiphile function compound and deionized water again; With calcium hydroxide supersaturated solution or calcium carbonate oversaturated solution the rock with last functional groups is carried out osmotic treated then; Calcium hydroxide can be because of generating lime carbonate with carbon dioxide reaction, and calcium carbonate oversaturated solution can be separated out lime carbonate because of the evaporation of moisture content..Under the inducing of organic formwork functional group, lime carbonate can form the growth of nucleus and crystallographic orientation more in an orderly manner, generates the biomineralization thing of lime carbonate in the surface of calcic rocks and micro chink.Constantly repeat the processing of organic formwork solution-treated and calcium ion supersaturated solution; lime carbonate biomineralization thing is constantly piled up and growth; make the micro chink of loose rocks obtain filling, the top layer covers goes up lime carbonate biomineralization layer, makes loose calcic rock obtain reinforcing and protection thus.
Key of the present invention be on the lime carbonate rocks, generate with the substrate material basic identical, and the lime carbonate biomineralization layer that can regulate and control of microtexture.
For the lime carbonate biomineralization layer that makes generation combines with basement rock firmly, at first to rock surface be cleaned up with clean-out system.Clean-out system of the present invention can be used deionized water, also can use organic solvent.Wherein the effect of organic solvent reduction rock surface energy is better, and lower surface energy helps adhering to of back organic formwork.Relatively environmental protection and cheap organic solvent are low-carbon alcohol, and low-carbon alcohol is ethanol, propyl alcohol, butanols, amylalcohol and their isomer, wherein ethanol the best.
In order to regulate and control the growth of calcium carbonate crystal, need to use amphipathic organic formwork, the amphiphile function compound that can be used as template has tensio-active agent, organic polymer and biomacromolecule.The used biological amphiphile function compound of the present invention is biological mucopolysaccharide, as chondroitin sulfate and amylopectin etc.; Also available phosphatide is as Yelkin TTS; And collagen protein etc.Perhaps replace, for example replace amylopectin with glutinous rice with the natural biological material that contains these biological amphiphile function compounds; Replace chondroitin sulfate with gelatine; Replace collagen protein etc. with Ovum Anas domestica album.Organic formwork solution is that above-mentioned functional compound or the natural biological material that contains these compounds are mixed with mass percent with deionized water is 0.1%～10% solution.Use which kind of functional compound to require to select according to reinforcing.
The mineral ion that forms calcium carbonate crystal is calcium ion and carbanion.In order to improve the formation speed of calcium carbonate crystal, and do not influence the perviousness of solution, the present invention mainly uses calcium hydroxide supersaturated solution or calcium carbonate oversaturated solution.Calcium carbonate oversaturated solution is ionic calcium soln and a carbanion solution of preparing earlier finite concentration (as 0.01mol/L) respectively, they slowly are added drop-wise to respectively in the appropriate amount of deionized water, the molecular ratio that need control suitable calcium ion and carbanion during dropping is about 1: 1 again.Similarly, the preparation of calcium hydroxide supersaturated solution is as long as change carbanion into hydroxide ion; In addition, if when not wishing to bring into other ions, also can directly use aqua calcis to concentrate and obtain.Above-mentioned ionic calcium soln can be with the water-soluble salt of strongly-acid preferably, for example calcium chloride preparation; Above-mentioned carbanion solution can be used preparations such as bicarbonate of ammonia, salt of wormwood; Above-mentioned hydroxide ion solution can be used preparations such as potassium hydroxide, sodium hydroxide; It is that just the calcium hydroxide solid is dissolved in deionized water that above-mentioned direct use aqua calcis concentrates, and the saturated solution that leaches is evaporated part moisture content obtains.The calcium hydroxide supersaturated solution or the calcium carbonate oversaturated solution that prepare can directly use, and also can filter the back and use, be good to filter the back result of use, because removed bad nucleus of crystal.In addition, can also take turns directly with ionic calcium soln and carbanion solution with the rock surface effect of going up functional groups, during same concentrations, be good to be pre-mixed and to cross filterable supersaturated solution action effect.
The pre-treatment of organic formwork solution has made on the rock surface band functional groups, when calcium hydroxide supersaturated solution or calcium carbonate oversaturated solution and rock surface are done the time spent, functional groups in calcium ion and the amphiphile, amphiphilic molecule forms a kind of coordination structure, electronegative active group energy chelating calcium ion, make calcium ion become the chemical combination attitude by free state, thereby calcium ion has higher local concentration near the amphiphile, amphiphilic molecule main chain, and other position calcium ion concns reduce relatively, make thus calcium carbonate crystal can only be on specific site nucleation and the growth of orientation ground is arranged, the biomineralization thing of formation lime carbonate.Constantly repeat the treating processes of above-mentioned organic formwork solution-treated and inorganic supersaturated solution; can use the organic formwork solution-treated earlier; after treating substantially dry; use calcium hydroxide supersaturated solution or calcium carbonate oversaturated solution osmotic treated again; also can be earlier with after organic formwork solution and 1: 0.5 by volume～3 mixing of inorganic supersaturated solution; handle with mixing solutions; treat to handle once more behind the substantially dry; the each processing all requires to treat the moisture content substantially dry; lime carbonate biomineralization thing just can constantly be piled up and ordering growth in rock surface and hole like this, and forming with lime carbonate is the reinforcement protection layer of main component.The filling covering effect of the cohesive action of organic formwork material and calcium carbonate crystal, and the synergy of microstructure improved jointly loose rocks intensity.
The operation of the various solution of the present invention can be used methods such as brushing, spray, immersion.
Advantage of the present invention: 1) reinforce lime carbonate class loose rocks with the biomineralization thing of lime carbonate, protecting materials is identical with the base material attribute, and consistency is good, does not change the composition of former historical relic, is likened to: " feldspar head on the stone "; 2) used organic formwork solution and the inorganic supersaturated solution for the treatment of processes all is transparent aqueous solution, can infiltrate into the certain depth of loose rocks, can not resemble other inorganic protecting materialss and to form duricrust on the surface; 3) the biomineralization film of Sheng Chenging is pure translucent, does not influence the glossiness on geological diagnostics surface, does not change outward appearance, color and the feel of protected stone cultural artifact; 4) lime carbonate biomineralization thing and organic formwork are filled and adhesion rock microfissure with certain microstructure, and the intensity of loose rocks and soaking-resistant ability are strengthened; 5) lime carbonate biomineralization thing is successively inserted the rock microporosity and covered the top layer, and is at first destroyed when running into extraneous the corrosion not with protected base material generation chemical reaction, can play and reinforce and the protection dual function; 6) lime carbonate is very stable mineral compound, does not have the yellowing on ageing problem of organic polymer protective membrane; 7) calcium carbonate crystal has reduced the porosity and the irregularity degree of rock in loose rocks surface coverage film forming, and anti-pollution characteristic is improved; 8) used various chemical feedstocks is harmless, the non-environmental-pollution problem.
Below in conjunction with embodiment the present invention is elaborated.
Embodiment
Embodiment 1
(1) formulations prepared from solutions
Calcium hydroxide supersaturated solution: accurately take by weighing CaCl
20.055g, be dissolved in the 50ml deionized water, be made into the 0.01mol/L ionic calcium soln; Accurately take by weighing NaOH 0.040g again, be dissolved in the 50ml deionized water, be made into 0.01mol/L hydroxide ion solution; Respectively get above-mentioned solution 10ml, slowly drip in the 500ml deionized water, constantly stir gently, be made into the supersaturation aqua calcis, obtain as clear as crystal calcium hydroxide supersaturated solution after filtering.
Organic formwork solution: take by weighing amylopectin 3g, put into the 250mL beaker, add the water of 100mL, heated and boiled 6 hours removes by filter insolubles, adds water quantitatively to 100mL, obtains amylopectin organic formwork solution.
(2) preparation of lime carbonate class loose rocks surface lime carbonate biomineralization back-up coat
Earlier with clear water flush away marble surface floating dust; Make clean-out system clean surface and drying once more with ethanol; Spray the amylopectin organic formwork solution for preparing in advance then, make it at marble surface uniform distribution naturally osmotic; After treating solution substantially dry film forming, spray the calcium hydroxide supersaturated solution for preparing again, make its uniform distribution naturally osmotic equally.After the drying, can observe marble surface by Electronic Speculum SEM and generate the lime carbonate biomineralization film that one deck has ad hoc structure, have nano level microstructure; Show that by diffraction XRD detection resultant mainly is the calcite crystallization.Constantly repeat the treating processes of organic formwork solution and calcium hydroxide supersaturated solution, the biomineralization film can constantly thicken, and fills the microfissure of rock and covers whole surface, makes loose marble obtain reinforcing and protection.The lime carbonate biomineralization back-up coat that obtains thus combines closely with the rock substrate; Do not influence color, feel and the glossiness of former marble surface; Loose marmorean resistant (ink) performance and surface hardness are improved; The weather resisteant of back-up coat and having good stability, making method is simple, is convenient to field operation, and is with low cost.
(3) fastening strength detects
For the consolidation effect that characterizes directly perceived, 75g particulate state (100 orders sieve) lime carbonate and 75g whiting (1000 orders sieve) are mixed with 15mL water, place in the stainless steel cylinder mould of 40mm * 80mm size, clash into 50 compactings, naturally placed 7 days under the room temperature, the gained sample is as loose marmorean imitated sample, and promptly blank is copied sample.
Penetration reinforcement effect: slowly drip infiltration 15mL equal-volume blended amylopectin organic formwork solution and calcium hydroxide supersaturated solution at the imitated sample surfaces of blank, naturally place after 7 days under the room temperature, the unguyed preceding blank sample of compressive strength rate that records the penetration reinforcement sample improves more than 13 times, surface hardness improves more than 5 times, and soaking-resistant reached more than 120 days.
The mixed reinforcement effect: used 15mL water in the time of will making blank imitated sample, replace with 15mL isopyknic amylopectin organic formwork solution and calcium hydroxide supersaturated solution, directly mix with calcium carbonate granule and powder and reinforce.The unguyed preceding blank sample of compressive strength rate that records the mixed reinforcement sample improves more than 14 times, and surface hardness only improves about 1 times, and soaking-resistant reached more than 120 days.
Embodiment 2
With example 1, just in cleaning, marble surface makes sanitising agent with propyl alcohol without ethanol, and all detection performances and example 1 are basic identical as a result.
Embodiment 3
With example 1, just in cleaning, marble surface makes sanitising agent with deionized water without ethanol, Electronic Speculum SEM observations shows that the particle tip of lime carbonate biomineralization thing of generation is big, the acid resistance of sample and resistance to soiling and example 1 are basic identical, and just the tack of biomineralization thing on basement rock reduces.
Embodiment 4
With example 1, the amount of used amylopectin when just changing preparation organic formwork solution, promptly take by weighing amylopectin 1g, 2g and 4g respectively, the result record the ultimate compression strength of the imitated sample of penetration reinforcement and surface hardness all ratio 1 in various degree reduction is arranged, explanation is near 3% amylopectin concentration, and fastening strength has maximum value.
Embodiment 5
With example 1, consider that the composition more than 90 percent is an amylopectin in the glutinous rice, the used amylopectin of preparation organic formwork solution is replaced with glutinous rice, the ultimate compression strength and the surface hardness ratio 1 that found that the imitated sample of penetration reinforcement decrease, and the ultimate compression strength of mixed reinforcement sample and surface hardness increase.Reason may be that the molecular weight of glutinous rice is bigger, and depth of penetration is not as good as amylopectin.
Embodiment 6
With example 1, just will prepare the used amylopectin of organic formwork solution and change the other biological amphiphile, amphiphilic molecule respectively into.Respectively with chondroitin sulfate, collagen protein, Yelkin TTS, gelatin preparation organic formwork solution.Electron microscopic observation has nothing in common with each other to the microscopic appearance and the granular size of the lime carbonate that generates as a result.Blank sample before the compressive strength rate of penetration reinforcement sample is unguyed improves about 8 times, 6 times, 5 times and 4 times respectively; Surface hardness also increases respectively, but the order of magnitude that improves is all below 2 times.Blank sample before the compressive strength rate of mixed reinforcement sample is unguyed improves about 15 times, 8 times, 6 times and 5 times respectively; The improvement value of surface hardness is also all below 2 times.Discovery in addition, the soaking-resistant that is participated in the reinforcing sample by chondroitin sulfate, Yelkin TTS, gelatin is better, all can stand the water logging bubble more than 120 days, and the soaking-resistant of collagen protein participation reinforcing sample is relatively poor relatively.Therefore, can regulate and control lime carbonate biomineralization layer with different biological amphiphile, amphiphilic molecules as required in the practical application.
Embodiment 7
With example 1, just change the calcium hydroxide supersaturated solution into calcium carbonate oversaturated solution.The preparation method of calcium carbonate oversaturated solution is: accurately take by weighing CaCl
20.055g, be dissolved in the 50ml deionized water, be made into the ionic calcium soln of 0.01mol/L; Accurately take by weighing Na again
2CO
30.053g, be dissolved in the 50ml deionized water, be made into 0.01mol/L carbanion solution; Above-mentioned two solution are respectively got 10ml, slowly drip in the 500ml deionized water, constantly stir gently, obtain calcium carbonate oversaturated solution.The result is: no matter be the penetration reinforcement sample, or the mixed reinforcement sample, the observed value of ultimate compression strength and surface hardness is all low than the sample that is obtained by the calcium hydroxide supersaturated solution.
Embodiment 8
With example 1, just the preparation with the calcium hydroxide supersaturated solution changes into Ca (OH)
2Solid is dissolved in the deionized water, filters out not dissolved solids, removes part moisture content with boulton process then, obtains the calcium hydroxide supersaturated solution more after filtration.As a result, all observations and measuring result are all basic identical with example 1.
Embodiment 9
With example 8, just do not use the concentration process of calcium hydroxide saturated solution, and with the thin pulp of calcium hydroxide.The preparation method of calcium hydroxide thin pulp be respectively will be more excessive 1～5 times than saturation solubility Ca (OH)
2Mix with deionized water, replace the calcium hydroxide supersaturated solution to use behind the stirring pulping.The result can be with Ca (OH) after the marble surface coating is dried
2The raising rock surface of concentration presents more and more whiter and thick more settled layer, has changed the outward appearance of geological diagnostics.
Embodiment 10
With example 1, just when imitated loose marble sample, replace calcium carbonate granule with yellow sand, replace calcium carbonate powders with laterite.All ratio 1 raisings of the ultimate compression strength of penetration reinforcement sample and mixed reinforcement sample as a result; And the surface hardness of sample and example 1 are more or less the same.
Embodiment 11
With example 1, just when marble surface prepares lime carbonate biomineralization back-up coat, earlier organic formwork solution and calcium hydroxide supersaturated solution were mixed in 1: 1 by volume, handle with the mixing solutions spray again, treat to handle once more behind the substantially dry, repeatedly repeat.As a result, all observations and measuring result are all basic identical with example 1.
Claims (10)
1. the lime carbonate biomineralization reinforcing method of a lime carbonate class stone cultural artifact, the biomineralization thing material of the lime carbonate of controlled architecture, the stone cultural artifact of reinforcement protection lime carbonate class, its step comprises:
Rock surface is cleaned up as clean-out system with deionized water or organic solvent low-carbon alcohol;
With biological amphiphile function compound and deionized water, be 0.1%～10% to be hybridly prepared into organic formwork solution by mass percentage;
Organic formwork solution pre-treatment rock surface with being mixed with makes the surface be with functional groups;
Supersaturated solution with calcium hydroxide or lime carbonate carries out osmotic treated to the rock with last functional groups then, and lime carbonate is induced nucleation and crystallographic orientation growth under the control of functional group;
Repeat the processing of organic formwork solution-treated and calcium ion supersaturated solution, lime carbonate biomineralization thing is constantly piled up and growth, and generating with lime carbonate on the loose rocks top layer is the biomineralization reinforcement protection layer of main component.
2. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 1 is characterized in that said low-carbon alcohol is a kind of of ethanol, propyl alcohol, butanols, amylalcohol and their isomer.
3. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 1 is characterized in that said amphiphile function compound is respectively solution a kind of of biological mucopolysaccharide, phosphatide, collagen or other bio-surfactant.
4. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 3, it is characterized in that said biological mucopolysaccharide is amylopectin or chondroitin sulfate, phosphatide is Yelkin TTS, and collagen is collagen protein, and other bio-surfactant is a gelatin.
5. according to the lime carbonate biomineralization reinforcing method of claim 3 or 4 described lime carbonate class stone cultural artifacts, it is characterized in that said amphiphile function compound, employing contains the crude substance of biological amphiphile function compound, comprising: replace amylopectin with glutinous rice; Replace chondroitin sulfate with gelatine; Replace collagen protein with Ovum Anas domestica album.
6. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 1, the supersaturated solution that it is characterized in that said calcium hydroxide is to be mixed by ionic calcium soln and hydroxide ion solution dilution, perhaps directly aqua calcis is concentrated to form; The supersaturated solution of lime carbonate is to be mixed by ionic calcium soln and carbanion solution dilution.
7. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 6 is characterized in that said ionic calcium soln is that strongly-acid salt is calcium chloride with the water-soluble salt of strongly-acid preferably preparation; Said carbanion solution is with preparations such as bicarbonate of ammonia, salt of wormwood; Said hydroxide ion solution is with potassium hydroxide, sodium hydroxide preparation; Said directly aqua calcis being concentrated is that the calcium hydroxide solid is dissolved in deionized water, and the saturated solution that leaches is evaporated part moisture content.
8. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 1, it is characterized in that said use clean-out system, organic formwork solution, calcium hydroxide supersaturated solution or calcium carbonate oversaturated solution, the working method that rock is handled is to adopt the operating method of brushing, spray, immersion.
9. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 1, it is characterized in that the processing of said repetition organic formwork solution-treated and calcium ion supersaturated solution, use earlier the organic formwork solution-treated, after treating substantially dry, use calcium hydroxide supersaturated solution or calcium carbonate oversaturated solution osmotic treated again, repeatedly repeat.
10. the lime carbonate biomineralization reinforcing method of lime carbonate class stone cultural artifact according to claim 1, it is characterized in that the processing of said repetition organic formwork solution-treated and calcium ion supersaturated solution, earlier with after organic formwork solution and 1: 0.5 by volume～3 mixing of inorganic supersaturated solution, handle with mixing solutions, treat to handle once more behind the substantially dry, repeatedly repeat.
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| CN102617111A (en) * | 2011-11-04 | 2012-08-01 | 云南大学 | Method and device for detecting reinforcement effect of stone and stone relic reinforcing agent |
| CN101343191B (en) * | 2008-08-26 | 2012-10-17 | 浙江大学 | Permeation type hydraulic stone cultural relics reinforcing material and reinforcing method |
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| CN112194504A (en) * | 2020-09-25 | 2021-01-08 | 安徽锂飞新材料科技有限公司 | Calcium hydroxide solution for protecting stone cultural relics and preparation method and application thereof |
| CN112194504B (en) * | 2020-09-25 | 2022-05-03 | 安徽锂飞新材料科技有限公司 | Solution for protecting stone cultural relics and preparation method and application thereof |
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