CN106116424A - A kind of stone cultural artifact shallow top layer repair materials and restorative procedure - Google Patents
A kind of stone cultural artifact shallow top layer repair materials and restorative procedure Download PDFInfo
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- CN106116424A CN106116424A CN201610451048.3A CN201610451048A CN106116424A CN 106116424 A CN106116424 A CN 106116424A CN 201610451048 A CN201610451048 A CN 201610451048A CN 106116424 A CN106116424 A CN 106116424A
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- top layer
- shallow top
- cultural artifact
- stone cultural
- repair materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention proposes a kind of stone cultural artifact shallow top layer repair materials, and including inorganic solution and low activity breeze, described inorganic solution includes potassium silicate solution, deionized water, solid potassium hydroxide, potassium fluosilicate, sodium lignin sulfonate and Borax.The present invention utilizes low activity breeze under certain condition; can react with specific inorganic solution; and during slow hardening; form compact structure, good weatherability, the firming body that fine structure is similar to rock and final strength is similar to shallow top layer rock mass, it is possible to be combined with the body close and firm of stone cultural artifact; see the most external with shallow mantle rock is mated; thus meet the requirement that historical relic's protection is reinforced, solving existing low activity slag cannot utilize, the defect polluting and wasting after discarding.
Description
Technical field
The present invention relates to repairing stone relics material and restorative procedure, repair material particularly to a kind of shallow top layer of stone cultural artifact
Material and restorative procedure.
Background technology
The Cave Temple, as the Typical Representative of stone cultural artifact, occupies extremely important status in China's historical and cultural heritage,
There is storage abundant, with a long history, have a very wide distribution, be worth prominent feature.A few days ago, just success is lost in Shen, the Silk Road, its
In be positioned at 22 within Chinese territory Shen and lose in point, just have Maijishan Grottoes, Crottoes at bvingling Monastery in Gansu Province, Bin County Giant Buddha Temple rock cave, Ke Zier
At rock cave etc. 4, so far, the five big Cave Temples such as China Mogao Grottoes, the Longmen Grottoes, Yungang Grottoes, Maijishan Grottoes, Crottoes at bvingling Monastery in Gansu Province
All rank World Cultural Heritage List.And in seven batches of key historical sites under state protection of China, the Cave Temple and stone inscription reach altogether
At 268, account for state and protect sum 6.25%.The Cave Temple reveals throughout the year puts field, is acted on by the factor such as natural force and artificial destruction,
Face the problems such as top layer damaged, shallow disease growth, the serious threat safe storage of these rare cultural relics of rock cave.For these stone
The degradation mechanism at temple, cave and Protective strategy, starting stage concern Grottoes is composed and is deposited Rock Slide Stability sex chromosome mosaicism and big scale of construction crag
The reinforcement for rushing danger of body, and the most aobvious for directly affecting the shallow top layer rock mass stability problem of the original style and features of rock cave and durability
Obtain the most prominent.
Grottoes is composed the shallow top layer rock mass deposited and is peeled off rapidly under various natural causes and structural agent effect, right
The safe storage of the historical relic in rock cave causes greatly threat, if these problems can not obtain the safest solution will
The cultural heritage of China is caused irremediable loss.The damage of shallow top layer rock mass deteriorates the mechanical property to rock mass, contraction
There is impact in performance and transmission performance etc..Shallow top layer rock mass plays protective action to total, and rock mass is tied by environmental factors
The physics of structure, chemical erosion are mostly from the beginning of surface.The damage deterioration of the most shallow top layer rock mass has emphatically with the durability of structure
It is related to.At present, the research that the shallow-layer of the Cave Temple and top layer are carried out because of spallation problems that structural damage causes is relatively fewer, is also
The principal element that in restriction rock cave protection, shallow surface layer peeling disease is effectively administered.
At present, industrial residue is that kind is many, quantity is big, with serious pollution rich and influential family, it is necessary to comprehensively analyzes, develop, profit
With.Present stage focuses primarily upon the admixture as cement and concrete for the comprehensive utilization of slag.But it is being applied to cement
Time in concrete, it is necessary to meet in national standard to the requirement of its lowest activity (according to GB/T18046-2008 " for cement and
Ground granulated blast furnace slag in concrete " detection, its 7d activity index minima is 75).Jiayuguan is the 12 of Gansu Province
One of individual prefecture-level city, is to have developed along with the construction of country's " First Five-Year Plan " key construction project " Jiuquan Iron & Steel Co. " for 1958
The city come.But during Jiayuguan steel and iron industry develops rapidly, produce the slag the like waste of enormous amount,
Owing to Technology and equipment are more backward, the slag of discharge is through extensively investigation, and its activity is the lowest, less than Standard, it is impossible to make
For the admixture in cement concrete, therefore, its utilization rate is the lowest.Through literature search, the most also do not have low activity slag
The technology effectively utilized.But owing to slag containing the element being much applicable to ground matter historical relic's protection, therefore, can be by ore deposit
Slag is applied in ground matter cultural relic protection project.
Summary of the invention
The present invention proposes a kind of stone cultural artifact shallow top layer repair materials and restorative procedure, utilizes low activity breeze necessarily
Under the conditions of, it is possible to react with specific inorganic solution, and during slow hardening, form compact structure, good weatherability, micro-
The firming body that fine texture is similar to rock and final strength is similar to shallow top layer rock mass, it is possible to the most firm with the body of stone cultural artifact
Consolidation is closed, and see the most external with shallow mantle rock is mated, thus meets the requirement that historical relic's protection is reinforced, and solves existing low activity ore deposit
Slag cannot utilize, the defect polluting and wasting after discarding.
The technical scheme is that and be achieved in that:
A kind of stone cultural artifact shallow top layer repair materials, including inorganic solution and low activity breeze, described inorganic solution includes
Potassium silicate solution, deionized water, solid potassium hydroxide, potassium fluosilicate, sodium lignin sulfonate and Borax.
Further, ash rock dust is also included.
Further, in described inorganic solution alkali silicon than for 1:1.2～1:1.4.
A kind of stone cultural artifact shallow top layer restorative procedure, comprises the following steps: clear up shallow top layer rock cranny → Selective filling
Bonding → the slip casting of adhesive spots → moistening bonding plane → fill is bonding → removing surface.
Beneficial effects of the present invention:
1, make full use of discarded low activity slag as the raw material repaired, solve discarded after pollute and waste
Defect, tool energy-conserving and environment-protective and the advantage reducing repairing cost.
2, the repair materials of the present invention selects the raw material of different ratios, and setting time is different, by regulation material rate,
Reach different setting times, be adapted to the requirement of different engineer applied.
3, the present invention is used for repairing stone cultural artifact, has high adhesive strength with stone cultural artifact, it is possible to stone matter after condensation
The body close and firm of historical relic combines, and after condensation, self comprcssive strength is the highest, and final strength is similar, therefore to shallow top layer rock mass
Good endurance, anti-destructive is strong.
4, the water absorption rate after the repair materials of the present invention condenses, well below ordinary cement, shows that repair materials compares after condensing
Cement is the finest and close, more stable, and durability is more preferable.
5, after the repair materials condensation of the present invention, see external with shallow mantle rock is mated, thus meets wanting of historical relic's protection reinforcing
Ask.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to
Other accompanying drawing is obtained according to these accompanying drawings.
Fig. 1 is TG curve chart；
Fig. 2 is SL infrared spectrogram；
Fig. 3 is SL-7d infrared spectrogram；
Fig. 4 is27Al nuclear magnetic spectrum figure；
Fig. 5 is comprcssive strength schematic diagram；
Fig. 6 is adhesive strength schematic diagram；
Fig. 7 is water absorption rate comparison diagram；
Fig. 8 is thermal dilatometry figure.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
For make the technical performance feature of this invention and application effect more preferably in understanding, mainly actual from laboratory test and outdoor
Engineer applied two aspect is expanded on further the performance characteristics of this invention.
One, the dependence test of stone cultural artifact shallow top layer repair materials
Use potassium silicate solution, deionized water, solid potassium hydroxide, potassium fluosilicate, sodium lignin sulfonate and Borax preparation
Good inorganic solution, static 24h, low activity breeze slowly to be poured in exciting agent, limit bevelling stirs, and after pouring into completely, quickly stirs
After mixing 2min die-filling.Form removal after 20 DEG C of lower seal maintenance 7d.Test specimen is broken into pieces, agate mortar adds ethanol levigate to regulation
After fineness, in vacuum drying oven, vacuum 0.4, to dry 24h under the conditions of 50 DEG C, obtain powder sample, named SL-7d is carried out
Subsequent experimental.Additionally choosing single low activity breeze, named SL does contrast test.
1, TGA test
By SL and SL-7d, carrying out TGA test, obtain TG curve chart 1, as seen from Figure 1, SL only has 600 DEG C～700
A DEG C exothermic peak, in this interval, weight loss is the 1.87% of raw material gross mass.There are three exothermic peaks in SL-7d: 120 DEG C of left sides
Right weightless peak, accounts for the 11.2% of gross mass；The weightless peak of about 300 DEG C, accounts for the 3.47% of gross mass；About 600～800 DEG C
Weightless peak, account for the 2.47% of gross mass.Wherein the weightless peak of about 600～800 DEG C is identical with the peak in raw material, Ke Nengwei
Calcium carbonate or intergranular in raw material combine water；110 DEG C and about the 300 DEG C combination water being respectively newly-generated product and constitution water
The weightlessness sloughed and cause.
2, IR test
By SL and SL-7d, carry out IR test, obtain infared spectrum Fig. 2 and Fig. 3, the characteristic peak correspondence official's energy occurred in figure
Group is shown in Table 1.
Table 1 characteristic peak positions and corresponding group
By Fig. 2 and Fig. 3 it can be seen that the IR of SL occurs obvious CaCO3Middle Ca-O characteristic peak.The strongest feature on spectral line
The wave number that peak is corresponding is 956cm-1And 1430cm-1And after reacting, the highest peak on the IR spectral line of SL-7d becomes
956cm-1And 1456cm-1, show 1430cm in course of reaction-1Peak at wave number moves to high wave number direction, and 956cm-1Not yet
It is moved.CaCO3In characteristic peak Ca-O characteristic peak move to high wave number, it may be possible to calcium carbonate reacts with solution,
Ca-O local environment or structure is caused to change.On spectral line, wave number is 482cm-1And 771cm-1The stretching vibration of corresponding Si-O
Peak and in-plane bending vibration peak, along with the carrying out of reaction, this peak all moves to lower wave number direction, shows to be probably in breeze
Si-O-Si chain owing to reacting, part AlO4It is replaced.
3, NMR test
Using Varian company of U.S. Inova600 type resonance instrument, magnetic field intensity is 14.1T.Measure29Si solid state nmr is altogether
Shaking time spectrum, Magic angle spinning (magic-angle spinning, MAS) rotating speed is 6kHz, and scanning times is 2048 times,29Si resonates
Frequency 119.148MHz, chemical shift external standard is tetramethylsilane.Measure27Al nuclear magnetic resonance, NMR time spectrum, evil spirit angle rotating speed is
12KHz, scanning times is 1024 times,27Al resonant frequency 156.3MHz, pulse width 0.5 μ s, with [Al (H2O)6]3+Do external standard.
SL's and SL-7d27Al nuclear magnetic spectrum is as shown in Figure 4.
As seen from Figure 4, in SL, the chemical environment of Al is mainly centered by 56.4 × 10-6ppm, and 20～80 × 10-
In the range of 6ppm, pentacoordinate Al phase is constituted mutually.In SL-7d, the absworption peak of Al phase offsets respectively to both sides, has both been formed with 9.8 × 10-
Hexa-coordinate centered by 6ppm, forms again the four-coordination centered by 73.5 × 10-6ppm.
After reaction, the shared component of each coordination is as shown in table 2.
Each coordination aluminum shared component mutually in table 2 SL product
In SL-7d 73.5 × 10-6The four-coordination component of ppm is significantly more than 9.8 × 10-6The hexa-coordinate of ppm, therefore reaction is produced
Thing is still based on four-coordination.
SL's and SL-7d29Si nuclear magnetic spectrum is as shown in Figure 5.
As seen from Figure 5, in SL-7d, the chemical environment of Si is mainly with-72.9 × 10-6Centered by ppm ,-90～-60
×10-6Exclusive state Q in the range of ppm0Constitute.After reacting, Si gradually aggregates into Q1(-77.6 × 10-6ppm) or Q2(-
81.310-6ppm).Show that in breeze, Si can react under the conditions of alkali-activated carbonatite.
After reaction, the shared component of each coordination is as shown in table 3.
Each coordination aluminum shared component mutually in table 3 SL product
In SL-7d-77.6 × 10-6The Q of ppm1Component is significantly more than Q2With remaining Q0, therefore product is with Q1It is main.
Two, the performance test of stone cultural artifact shallow top layer repair materials
Prepare stone cultural artifact shallow top layer repair materials, and with reference to about specification, its performance being used for when repairing is carried out system
Test, including outward appearance, intensity, setting time, adhesive strength and water absorption rate etc..
Design experiment coordinates such as table 4 to be shaped testing:
Match ratio tested by table 4
1, patching material setting time
After shaping test piece, measure its setting time by consumptive use of water normal consistence, only by the examination of cement paste texturometer
Cone takes off, and changes a diameter of 1.1 millimeters, the test point of long 50 millimeters；During mensuration, from curing box, take out the round mould filling clean slurry,
It is placed under test point, makes test point contact with clean slurry face, tighten screw.The most suddenly loosen screw, allow test point freely sink to only starch, see
Examine total indicator reading.Only playing when test point sinks to only to starch glass plate 3-5 millimeter at the bottom of middle-range circle mould during self-watering, the time experienced is
Presetting period.Playing during self-watering and stop when being less than 0.5 millimeter during test point sinks to only starch to test point, the time experienced is final set
Time.Record setting time as shown in table 5.
Table 5 patching material setting time
As seen from the above table, the amount according to exciting agent is different, and setting time is different, by regulating setting time, permissible
Adapt to the requirement of different engineer applied.
2 comprcssive strength
After upper table shaping test piece, under the conditions of 40 DEG C, after wrapping up with preservative film, maintenance is to 7d, 14d, 28d, surveys its single shaft
Comprcssive strength, result such as table 6:
Table 6 patching material uniaxial compressive strength
Patching material intensity increases in time and dramatically increases, particularly 7d-14d, and during 14d, intensity is to repair material close to 7d
The twice of material intensity, but increases slowly after 14d.
3, patching material and rock mass adhesive strength
70.7 cube granite are averagely cut to two pieces, with patching material, two pieces are got up, at 20 DEG C along tangent plane bonding
Under the conditions of maintenance to after certain age, survey its jacking strength.
G1, G2, G3 hereinafter represents that material is repaired on the shallow top layer of stone cultural artifact of above-mentioned ML3, ML7, ML8 proportioning respectively
Material, C represents traditional portland patching material.
Adhesive strength is shown in Table 7:
Table 7 patching material and rock mass adhesion strength
From above chart, patching material and rock mass adhesive strength scope are 0.4～about 1.04MPa.
4, the water absorption rate of patching material
Water absorption rate refers to that test specimen freely sucks the quality of water and the ratio of test specimen dry mass under atmospheric pressure and room temperature condition.Full
Refer to that test specimen sucks the quality of water and the ratio of test specimen dry mass under high pressure or vacuum condition with water absorption rate.
After test piece maintenance extremely regulation age, after test specimen is dried 6h in 100 DEG C of baking ovens, weigh weight W1, be immersed in the water
After 24h, quality no longer changes, and after wiping surface moisture with dry towel, weighs weight W2, then test specimen is put into vacuum and satisfies water instrument
After middle vacuum dehydration 24h, quality no longer changes, and weighs weight W3.
Water absorption rate and saturated water absorption reflect the size of the open capillary porosity of material for test the most to a certain extent,
Can indirectly judge freezing and thawing performance and the impermeability of material.
G1, G2, G3 are carried out water absorption test, and experimental result is shown in Table 8 and Fig. 7.
The moisture content test of table 8 patching material
As seen from Figure 7, the water absorption rate of patching material, well below light water cement paste, shows that patching material has relatively
Cement paste is the finest and close, has less capillary porosity rate.
5, the thermal property of patching material
For probing into patching material and the concordance of rock mass thermal contraction performance under Service Environment, test its heat conductivity and line
The coefficient of expansion, and be analyzed in rock cave locality rock mass.Experiment uses HY4690 type wire expansion coefficient measuring instrument to measure measurement 0
DEG C～100 DEG C between strain, experimental result is shown in Table 9.
The linear expansion coefficient of table 9 stone powder patching material
By above chart it can be seen that the linear expansion coefficient of patching material and more mating of rock mass.
To sum up, low activity slag, after suitable chemical reaction, meets and the physical mechanics property of shallow top layer deterioration rock mass
The requirement that can match, and there is the permeability resistance being better than cement slurry, adhesive strength is higher, and material prescription is economic and environment-friendly,
Can be effectively used for shallow top layer deterioration rock mass is repaired.
Three, in actual use
Choose potassium silicate solution, deionized water, solid potassium hydroxide, potassium fluosilicate, sodium lignin sulfonate and Borax preparation
Inorganic solution, is subsequently adding low activity breeze and stirs.Ash rock dust can also be added.Alkali silicon ratio preferably 1 in inorganic solution:
1.2～1:1.4.
Applied at Maijishan Grottoes and Longshan Taoist Grottoes, omnidistance in strict accordance with: clear up shallow top layer rock cranny → choosing
Select the bonding → slip casting of filling adhesive spots → moistening bonding plane → fill bonding → flow process of removing surface carries out.
Indoor and on-the-spot test all confirms, the activity of low activity breeze is less than Standard, it is impossible to as cement concrete
The breeze of admixture, under certain condition, by reacting with specific inorganic solution, during slow hardening, forms knot
Structure is fine and close, good weatherability, the Seed harvest that fine structure is similar with rock and final strength mates with shallow top layer rock mass, it is possible to stone
The body close and firm of matter historical relic combines, and after reinforcing, see external with shallow mantle rock is mated simultaneously, is suitable for deteriorating shallow top layer rock mass
Reparation.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (5)
1. a stone cultural artifact shallow top layer repair materials, it is characterised in that include inorganic solution and low activity breeze, described inorganic
Solution includes potassium silicate solution, deionized water, solid potassium hydroxide, potassium fluosilicate, sodium lignin sulfonate and Borax.
2. the shallow top layer of stone cultural artifact as claimed in claim 1 repair materials, it is characterised in that also include ash rock dust.
3. the shallow top layer of stone cultural artifact as claimed in claim 1 repair materials, it is characterised in that the modulus of described potassium silicate solution
It is 3.8.
4. the stone cultural artifact shallow top layer repair materials as according to any one of claim 1-3, it is characterised in that described inorganic molten
In liquid, alkali silicon is than for 1:1.2～1:1.4.
5. a stone cultural artifact shallow top layer restorative procedure, it is characterised in that comprise the following steps: clear up shallow top layer rock cranny →
Bonding → the slip casting of Selective filling adhesive spots → moistening bonding plane → fill is bonding → removing surface.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470840A (en) * | 2020-04-23 | 2020-07-31 | 中国文化遗产研究院 | Stone cultural relic surface crack repairing material and preparation method thereof |
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| CN103708806A (en) * | 2013-12-23 | 2014-04-09 | 长安大学 | Inorganic modifier for historical site soil |
| CN105439525A (en) * | 2015-11-18 | 2016-03-30 | 长安大学 | Earthen archaeological site crack repairing agent and application thereof |
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| CN103265242A (en) * | 2013-05-24 | 2013-08-28 | 中铁西北科学研究院有限公司 | Mineral polymer grouting material and method for strengthening grotto surrounding rock fractures by using same |
| CN103708806A (en) * | 2013-12-23 | 2014-04-09 | 长安大学 | Inorganic modifier for historical site soil |
| CN105439525A (en) * | 2015-11-18 | 2016-03-30 | 长安大学 | Earthen archaeological site crack repairing agent and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111470840A (en) * | 2020-04-23 | 2020-07-31 | 中国文化遗产研究院 | Stone cultural relic surface crack repairing material and preparation method thereof |
| CN111470840B (en) * | 2020-04-23 | 2022-05-31 | 中国文化遗产研究院 | Stone cultural relic surface crack repairing material and preparation method thereof |
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Effective date of registration: 20200628 Address after: 730000 No. 365, East Democratic Road, Chengguan District, Gansu, Lanzhou Patentee after: Gansu China Railway Construction Engineering Co.,Ltd. Address before: 730000 No. 365 East Democratic Road, Gansu, Lanzhou Patentee before: NORTHWEST RESEARCH INSTITUTE Co.,Ltd. OF C R E C |