CN102515614A - High-performance cement concrete polycarboxylic liquid antifreezer - Google Patents
High-performance cement concrete polycarboxylic liquid antifreezer Download PDFInfo
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Abstract
The invention relates to high-performance cement concrete polycarboxylic liquid antifreezer which comprises polycarboxylic high-performance water reducing agent, organic alcohol amine, sodium formate, alcohol, an air entraining component, a defoaming component and water. The weight ratio of all the components is that: polycarboxylic high-performance water reducing agent: organic alcohol amine: sodium formate: alcohol: air entraining component: defoaming component: water = (60 to 250): (5 to 18): (0 to 12): (20 to 60): (0 to 25): (1 to 4): (550 to 710). Compared with the prior antifreezer, the high-performance cement concrete polycarboxylic liquid antifreezer has the advantages of no chloride ions, no ammonia release and low alkali content. When in the preparation, the defoamer is introduced, so that large bubbles on the surface of the polycarboxylic high-performance water reducing agent are eliminated. Simultaneously, the air entraining agent is added in, so that the gas content of concrete is adjusted to an appropriate amount, the strength of the concrete is improved and the concrete is more attractive.
Description
Technical field
The present invention relates to a kind of polycarboxylic acids anti-freeze agent that is used for cement concrete pumping in winter, belongs to building material technical field.
Background technology
Thereby concrete antifreezer is meant and can reduces ice crystal pressure through freezing point, the inhibition water freezing that reduces water; And quicken effect such as cement initial stage aquation and make concrete lasting aquation and sclerosis under subzero temperature, and be issued to a kind of concrete admixture of estimated performance at the regulation curing condition.China is vast in territory, in the middle and lower reach of Yangtze River, ground such as northeast, North China and the Inner Mongol, Qinghai, Xinjiang, winter temperature is all below-5 ℃, extreme temperature can be reduced to-40 ℃.If temperature is reduced to below the concrete hydrating water-ice point temperature; The serious aquation process of leather-silhouette show cement; Strength development does not slowly reach requirement in the length of time, and freeze to produce the ice expansive force concrete inner structure is destroyed, and gives concrete intensity and weather resistance deleterious impact.
Mainly take following several kind modes to solve concrete antifreeze problem when negative temperature concrete is constructed winter.1, improves the molding temperature of concrete mix, implement the insulation measure.Generally take the hot water mix, heating is gathered materials and concrete delivery truck installs modes such as thermal insulation layer additional.2, adopt outside heating method.Be lower than-10 ℃ for temperature, can with the heat transferred concrete or directly to the concrete heating, concrete be under the positive temperature condition through heating concrete member ambient air.3, add frostproofer disastrously.Because the construction of admixture frostproofer is simple, effect is also relatively good, therefore obtained to use widely in China.
Up to the present, the frostproofer that uses in the construction work both at home and abroad mainly is divided into two kinds, and one type is the early-strength type frostproofer, and one type is the anti-freeze type frostproofer.These two types all is to form with diminishing component, accelerating component, antifreezing component and bleed component.Wherein the diminishing component comprises high performance water reducing agent of polyocarboxy acid, naphthalene series high-efficiency water-reducing agent, melamine high-efficiency water-reducing agent, sulfonated lignin etc.Accelerating component mainly contains sodium sulfate, calcium chloride, nitrocalcite, trolamine etc.The bleed component mainly comprises wooden calcium, wooden sodium and rosin based air entrapment agent.Antifreezing component mainly contains calcium chloride, salt of wormwood, sodium-chlor, Sodium Nitrite and terepthaloyl moietie etc.
Patent CN102289293A asks for protection polycarboxylic acids anti-freeze agent that is used for cement concrete and preparation method thereof.It is to be formed by high-efficiency water-reducing agent of poly-carboxylic acid, organic alcohol amine, low-carbon alcohol, thiocyanate-, formate constituent optimization combining and configuring.The preferred proportion of each component is following: high-efficiency water-reducing agent of poly-carboxylic acid: organic alcohol amine: low-carbon alcohol: thiocyanate-: calcium formiate: water=(3.8-8.0): (0.5-2.0): (0.0-2.0): (10.0-20.0): (0.0-6.0): (65.0-75.0).(mass percent).The frostproofer of this system is compared with existing frostproofer, has higher water-reducing rate and serviceability preferably, and gain in strength is fast under the subzero temperature.Little, the no chlorine of volume in cement, alkali content are low, and early age strength of concrete and later strength are high.Be applicable to construction in north of china in winter-5 ℃～-20 ℃ scopes.
Patent CN102140021A asks for protection a kind of cement concrete frostproofer, is made up of following components by part by weight.15～30 parts of high performance water reducing agent of polyocarboxy acid, 20～30 parts of low mass molecule alcohols, 0.1～0.15 part of triterpenoid saponin, 50～70 parts in 10～30 parts of calcium formiates, 2～5 parts of organic alcohol amines and water.In this invention, triterpenoid saponin mainly plays the bleed effect, can form a large amount of fine bubbles, improves concrete frost heave stress.This invention can be-20～-30 ℃ of constructions down.
More than all used poly carboxylic acid as the diminishing component in two patents because poly carboxylic acid has the bleed effect, but the bubbles volume that poly carboxylic acid is introduced is big and the poor quality, so like this can be to concrete pore structure and weather resistance generation detrimentally affect.And the calcium ion in the calcium formiate can influence the water-reducing effect of poly carboxylic acid.
In this prescription, because polycarboxylate water-reducer will be introduced the poor quality of a large amount of bubble and bubble in use, so the bleed quality of this prescription has much room for improvement.
CN1153753 asks for protection efficient liquid antifreezerfor concrete; It is mixed by terepthaloyl moietie, urea, trolamine, sodium laurylsulfonate, high efficiency water reducing agent and six kinds of compositions of water and forms, and the weight constituent ratio of each component is: terepthaloyl moietie: urea: trolamine: sodium laurylsulfonate: high efficiency water reducing agent: water=(65～80) (16.5～30): (2.2～3.0): (1.3～2.0): (50～120): (50～370).It not only has good frost resistance, low alkali, free from chloride special brokeback, and have protect plasticity can be good, production technique is simple and be convenient to advantage such as automatic gauge.This admixture can be complementary with multiple admixture, cement and adulterant.Be applicable to that temperature is not less than-15 ℃ various concrete preparation.Contain urea in this frostproofer, after the concrete placement moulding, can discharge ammonia.
Goal of the invention
In order to overcome above-mentioned defective, the technical problem that the present invention will solve is: invent a kind ofly have diminishing, protect collapse, strong, antifreeze and liquid antifreezerfor concrete early with good air-entraining function.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following:
The polycarboxylic acids anti-freeze agent that is applicable to the cement concrete pumping of the present invention is characterized in that, is made up of high performance water reducing agent of polyocarboxy acid, organic alcohol amine, sodium formiate, low-carbon alcohol, bleed component, froth breaking component, water.Each composition weight constituent ratio is: high performance water reducing agent of polyocarboxy acid: organic alcohol amine: sodium formiate: low-carbon alcohol: the bleed component: the froth breaking component: water=(60～250): (5～18): (0～12): (20～60): (0～25): (1～4): (550～710).
Described skimmer is meant polyether-modified polysiloxane defoamers.
Described organic alcohol amine comprises trolamine, diethylolamine, tri-isopropanolamine.
Described bleed component comprises X 2073, sodium lauryl sulphate, sodium abietate.
Described low-carbon alcohol comprises terepthaloyl moietie, USP Kosher.
The poly carboxylic acid liquid frostproofer of the present invention's preparation selects it to form component from following several aspects.(1) water-reducing rate of increase frostproofer reduces wc.So just can under the frostproofer low-dosage, guarantee the concentration of antifreeze accelerating component, reduce the freezing point of inside concrete water.(2) select suitable skimmer and air entrapment agent to be used, introduce some polarity microbubbles.Increase small closed pores in the concrete, reduce the thermal conductivity of concrete mix and maturing so on the one hand, can help to reduce the ice crystal pressure that inside concrete moisture content freezes and produced on the other hand.(3) select suitable hardening accelerator, promote hydrated cementitious speed, accelerates concretely to condense, harden, make concrete early set up critical strength, the structure deteriorate effect of generation when the opposing internal moisture is icing.(4) selected component can reduce the freezing point of water, can destroy lattice structure again, reduces the destructiveness that water freezing causes.
High performance water reducing agent of polyocarboxy acid can be that the water requirement that concrete mix reaches the regulation denseness significantly reduces, and has so just reduced the quantity that can freeze water, but has improved the concentration of antifreezing component simultaneously, and the freezing point of water is further reduced.Add skimmer and can eliminate the unnecessary air pocket of concrete appearance, make concrete outward appearance more attractive in appearance, reduced concrete air content simultaneously and improved concrete pore structure and compaction rate, improved concrete weather resistance.Add suitable air entrapment agent in the time of froth breaking, in concrete, introduce quality bubble preferably.Select organic accelerating component, accelerate the aquation process of cement, thereby make concrete form the intensity skeleton at short notice.Organic antifreezing component of selecting not only has the effect that reduces freezing point, can also make the lattice structure gross distortion of ice, avoids forming the big ice crystal of frost heave stress.
Select above each component will fully take into account the consistency between each component, on action effect, will mutually promote, reach the effect of 1+1＞2.
The present invention has the following advantages:
The most outstanding advantage of the present invention is to have introduced skimmer, has eliminated the air pocket on high performance water reducing agent of polyocarboxy acid surface.Add air entrapment agent simultaneously, can concrete air content be adjusted to appropriate vol, increase concrete intensity and make concrete more attractive in appearance.
Concrete antifreezer of the present invention not chloride ion-containing, do not have that ammonia discharges, low alkali content.Use has high environmental protection using value and prevents alkali-aggregate reaction as frostproofer in concrete.For the important technology that develops green concrete and high performance concrete, high durability concrete winter construction is used.
The high-performance polycarboxylic acids water reducing agent that concrete antifreezer of the present invention uses has low-dosage, dissemination is strong, loss of slump is little, early strength strengthens and effect such as good endurance.Except improving concrete pore structure and compaction rate, can also control concrete slump through the time lose.Better control problems such as concrete slow setting, bleeding, bleed.
The invention provides a kind of more existing frostproofer bleed performance and better be used for cement concrete polycarboxylic acid series liquid frostproofer.
Be more detailed explanation various material compositions of the present invention, compound method and excellent results, enumerate the following example and test according to the performance index of building material industry standard JC457-2004 concrete antifreezer.But scope of the present invention is not limited only to following embodiment.
Embodiment:
Embodiment 1:
With reference to the synthetic high performance water reducing agent of polyocarboxy acid of following steps.Take by weighing the 98g maleic anhydride and add in 800mL 1,2 ethylene dichloride, be heated to 75 ℃ of dissolvings, add vinylbenzene 104g, Lucidol 5g, mercaptoethanol 2g is mixed in the separating funnel, splashes into there-necked flask.Drip off the back at 80 ℃ of reaction 2h, elevated temperature to 95 ℃ reacts 2h again.After the cooling, add sherwood oil, suction filtration, dry Zelan 338, it is x 44% that maleic anhydride gets content.The synthetic multipolymer is added 1, stirring and dissolving in the 2-ethylene dichloride, the SO3 that from oleum, newly steams is diluted in 1, splashes in the reaction solution in the 2-ethylene dichloride again, in 15min, dropwises, and continues at room temperature to react 2h.Product is with 1, and the washing of 2-ethylene dichloride is again with the anhydrous diethyl ether washing, in 50 ℃ of dry sulfonated phenylethylene copolymer-maleic anhydrides that get of vacuum drying oven.With poly glycol monomethyl ether 550 and sulfonated phenylethylene copolymer-maleic anhydride proportional mixing; Make that the maleic anhydride mol ratio is 1: 1 in poly glycol monomethyl ether 550 and the sulfonated phenylethylene copolymer-maleic anhydride; React 8h down at 100 ℃, obtain containing the co-poly carboxylic acid of Soxylat A 25-7 side chain.
Will be according to the method described above the synthetic polycarboxylate water-reducer to adjust to solid content be 40%.Take by weighing 180 gram high-efficiency water-reducing agent of poly-carboxylic acid and join in the Glass Containers, add entry 788 grams simultaneously, under whipped state, add trolamine 5 grams, sodium formiate 6 grams, terepthaloyl moietie 20 grams, polyether-modified polysiloxane defoamers 1 gram then respectively successively.Last component wants abundant stirring and dissolving even during a component after adding, obtains uniform liquid at last.
Embodiment 2:
Carrying out the synthetic of high-efficiency water-reducing agent of poly-carboxylic acid and adjust solid content according to embodiment 1 is 40%.Take by weighing 200 gram high-efficiency water-reducing agent of poly-carboxylic acid and join in the Glass Containers, add entry 768 grams simultaneously, under whipped state, add trolamine 5 grams, sodium formiate 6 grams, terepthaloyl moietie 20 grams, polyether-modified polysiloxane defoamers 1 gram then respectively successively.Last component wants abundant stirring and dissolving even during a component after adding, obtains uniform liquid at last.
Embodiment 3:
Carrying out the synthetic of high-efficiency water-reducing agent of poly-carboxylic acid and adjust solid content according to embodiment 1 is 40%.Take by weighing 220 gram high-efficiency water-reducing agent of poly-carboxylic acid and join in the Glass Containers, add entry 710 grams simultaneously, under whipped state, add diethylolamine 15 grams, terepthaloyl moietie 50 grams, sodium lauryl sulphate 3 grams, polyether-modified polysiloxane defoamers 2 grams then respectively successively.Last component wants abundant stirring and dissolving even during a component after adding, obtains uniform liquid at last.
Embodiment 4:
Carrying out the synthetic of high-efficiency water-reducing agent of poly-carboxylic acid and adjust solid content according to embodiment 1 is 40%.Taking by weighing 220 gram high-efficiency water-reducing agent of poly-carboxylic acid joins in the Glass Containers; Add entry 678 grams simultaneously, under whipped state, add diethylolamine 15 grams, sodium formiate 10 grams, USP Kosher 50 grams, X 2073 25 grams, polyether-modified polysiloxane defoamers 2 grams then respectively successively.Last component wants abundant stirring and dissolving even during a component after adding, obtains uniform liquid at last.
Implementation result:
1, flowing degree of net paste of cement and degree of mobilization through the time lose
Flowing degree of net paste of cement and degree of mobilization through time loss and degree of mobilization through the time measuring method that loses carry out according to " concrete admixture uniformity detection method " GB/T8077-2000.Test result is seen table 1
Table 1 flowing degree of net paste of cement and degree of mobilization through the time lose
| Frostproofer | Volume (%) | Initial flow degree (mm) | 1h degree of mobilization (mm) |
| Embodiment 1 | 2 | 240 | 230 |
| Embodiment 2 | 2 | 270 | 270 |
| Embodiment 3 | 2 | 290 | 285 |
| Embodiment 4 | 2 | 290 | 290 |
2, the low-temperature stability of obtaining liq frostproofer
The poly carboxylic acid frostproofer that will make according to the inventive method under-10 ℃ temperature freezing 24 hours is observed frostproofer and colour-change whether occurred, crystalline polamer whether occurs.The result sees table 2.
The low-temperature stability test-results of table 2 liquid frostproofer
| Frostproofer | Before freezing | After freezing |
| Embodiment 1 | Evenly no crystallization | No change |
| Embodiment 2 | Evenly no crystallization | No change |
| Embodiment 3 | Evenly no crystallization | No change |
| Embodiment 4 | Evenly no crystallization | No change |
3, the resistance to frost of preparation frostproofer
Poly carboxylic acid liquid frostproofer according to the inventive method preparation carries out the concrete batching Performance Detection.Concrete performance test detects each item performance index of fresh concrete and maturing respectively with reference to the regulation of JC475-2004 concrete antifreezer.Test temperature is carried out with-15 ℃ according to-10 ℃.
The normal concrete proportioning designs according to JGJ55, mixes concrete and the cement in the normal concrete proportioning, the sand of frostproofer, the constant rate of stone.The starting material that use are following: P.O42.5 ordinary Portland cement, fineness modulus are 2.9 medium sand, the rubble of 16～31.5mm.Proportioning should meet following provisions: the folk prescription concrete mix: cement amount 330kg, sand 730 kg, stone 1145 kg, admixture dosage are 1.5%～3%.
Water consumption should make concrete slump reach (80 ± 10) mm, and the water consumption of taking according to test is 175 kg.
The performance of concrete mix is measured and is calculated according to GB8076, and slump test should be accomplished in the 5min after concrete goes out machine.Normal concrete with examined that concrete sample should be made simultaneously, the making of concrete sample and maintenance should carry out according to GB/T50080; But mix and do not mix the frostproofer slump and reach (80 ± 10) mm; Test specimen adopts shaking table jolt ramming, and time of vibration is 10～15s.Mixing the concrete sample of frostproofer should be under (20 ± 3) ℃ envrionment temperature move in the refrigerator and with plastic cloth after according to the rules the time precuring and covers test specimen; Its envrionment temperature should evenly drop to specified temperature in 3～4h; The demoulding behind the maintenance 7d is thawed under (20 ± 3) ℃ envrionment temperature.Carry out compressive strength test after thawing or change normal curing.
The concrete performance of admixture polycarboxylic acids anti-freeze agent is shown in table 3 and table 4 under freezing-10 ℃ of conditions
Testing concrete performance result when table 3 volume is 2% curing temperature for-10 ℃
| Frostproofer | Water-reducing rate (%) | Time of coagulation | -7d（Mpa） | -7+28d（Mpa） | 28d（Mpa） | -7+56d（Mpa） |
| Blank | ---- | 390min/570min | ----- | ----- | 37.52 | ---- |
| Embodiment 1 | 21.0 | 310min/510min | 4.70 | 38.27 | 39.80 | 46.57 |
| Embodiment 2 | 23.3 | 300min/490min | 4.88 | 39.72 | 42.44 | 47.27 |
| Embodiment 3 | 25.7 | 335min/540min | 4.97 | 42.89 | 45.03 | 48.81 |
| Embodiment 4 | 25.2 | 320min/530min | 5.42 | 45.99 | 48.35 | 49.59 |
Different age strengths contrasts when table 4 volume is 2% curing temperature for-10 ℃
| Frostproofer | R -7(%) | R -7+28(%) | R 28(%) | R -7+56(%) |
| Embodiment 1 | 12.60 | 102.50 | 106.12 | 124.12 |
| Embodiment 2 | 13.10 | 105.88 | 113.10 | 126.00 |
| Embodiment 3 | 13.25 | 114.32 | 120.02 | 130.10 |
| Embodiment 4 | 14.46 | 122.57 | 128.89 | 132.17 |
The concrete performance of admixture polycarboxylic acids anti-freeze agent is shown in table 5 and table 6 under freezing-15 ℃ of conditions
Testing concrete performance result when table 5 volume is 2.5% curing temperature for-15 ℃
| Frostproofer | Water-reducing rate (%) | Time of coagulation | -7d（Mpa） | -7+28d（Mpa） | 28d（Mpa） | -7+56d（Mpa） |
| Blank | ---- | 410min/580min | ----- | ----- | 37.52 | ---- |
| Embodiment 1 | 22.0 | 300min/520min | 3.95 | 39.07 | 40.18 | 46.99 |
| Embodiment 2 | 24.3 | 320min/490min | 4.08 | 39.81 | 43.06 | 47.69 |
| Embodiment 3 | 25.5 | 340min/510min | 4.20 | 42.43 | 45.40 | 59.75 |
| Embodiment 4 | 25.7 | 310min/540min | 4.32 | 46.82 | 45.84 | 50.37 |
Different age strengths contrasts when table 6 volume is 2.5% curing temperature for-15 ℃
| Frostproofer | R -7(%) | R -7+28(%) | R 28(%) | R -7+56(%) |
| Embodiment 1 | 10.54 | 104.12 | 107.10 | 125.23 |
| Embodiment 2 | 10.87 | 106.12 | 114.76 | 127.10 |
| Embodiment 3 | 11.20 | 113.10 | 121.00 | 132.60 |
| Embodiment 4 | 11.53 | 124.81 | 122.19 | 134.25 |
Concrete other performance is as shown in table 7
The comparison of table 7 and frostproofer standard code performance
| Interventions Requested | Performance index (acceptable end product/salable product) | -10 ℃ of measured values | -15 ℃ of measured values |
| Water-reducing rate (%) >;= | 10 | 21.0～25.2 | 22.0～25.7 |
| Bleeding rate (%)<= | 80/100 | 21 | 26 |
| Air content (%) >;= | 2.5/2.0 | 2.7～3.4 | 2.6～3.3 |
| R -7(%)≥ | 12/10 | 12.6～14.46 | 10．54～11.53 |
| R -7+28(%)≥ | 95/85 | 102.50～122.57 | 104.12～124.18 |
| R 28(%)≥ | 100/95 | 106.12～128.89 | 107.10～122.19 |
Admixture the present invention prepares concrete negative temperature conservation (10 ℃ and-15 ℃) the intensity R of frostproofer
-7And subzero temperature changes each age strength of normal temperature maintenance except R
-7Surpass the requirement of the acceptable end product of the whole meet the specifications regulations of remaining index beyond the salable product.
More than the polycarboxylic acids anti-freeze agent that is used for cement concrete pumping in winter provided by the present invention has been carried out detailed introduction; A handy concrete example is set forth principle of the present invention and implementation method among this paper; Above instance is just for helping understand method of the present invention and core concept; On embodiment and range of application, all change to some extent, to sum up, this description should not be construed as limitation of the present invention.
Claims (6)
1. an a kind of high-performance cement series of polyocarboxy acid for concrete liquid frostproofer is characterized in that, is made up of high performance water reducing agent of polyocarboxy acid, organic alcohol amine, sodium formiate, low-carbon alcohol, bleed component, froth breaking component, water.
2. each composition weight constituent ratio is: high performance water reducing agent of polyocarboxy acid: organic alcohol amine: sodium formiate: low-carbon alcohol: the bleed component: the froth breaking component: water=(60～250): (5～18): (0～12): (20～60): (0～25): (1～4): (550～710).
3. high-performance cement series of polyocarboxy acid for concrete liquid frostproofer according to claim 1, it is characterized in that: described skimmer is meant polyether-modified polysiloxane defoamers.
4. high-performance cement series of polyocarboxy acid for concrete liquid frostproofer according to claim 1, it is characterized in that: described organic alcohol amine comprises trolamine, diethylolamine, tri-isopropanolamine.
5. high-performance cement series of polyocarboxy acid for concrete liquid frostproofer according to claim 1, it is characterized in that: described bleed component comprises X 2073, sodium lauryl sulphate, sodium abietate.
6. high-performance cement series of polyocarboxy acid for concrete liquid frostproofer according to claim 1, it is characterized in that: described low-carbon alcohol comprises terepthaloyl moietie, USP Kosher.
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| CN105985054A (en) * | 2016-01-15 | 2016-10-05 | 安徽鑫润新型材料有限公司 | Efficient water reducing agent for improving frost resistance and dispersibility of concrete |
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| CN104529232A (en) * | 2014-12-04 | 2015-04-22 | 同济大学 | Polycarboxylate composite water reducing agent used for high-carbon-content concrete, and preparation method and application method thereof |
| CN105503013B (en) * | 2015-12-22 | 2017-12-19 | 河南科之杰新材料有限公司 | A kind of liquid concrete early strength antifreezing agent and preparation method thereof |
| CN105503013A (en) * | 2015-12-22 | 2016-04-20 | 河南科之杰新材料有限公司 | Liquid concrete early strength anti-freezing agent and preparation method thereof |
| CN105985054A (en) * | 2016-01-15 | 2016-10-05 | 安徽鑫润新型材料有限公司 | Efficient water reducing agent for improving frost resistance and dispersibility of concrete |
| CN106396521A (en) * | 2016-08-31 | 2017-02-15 | 南通科达建材股份有限公司 | Early strength self restoration grouting material |
| CN109704629A (en) * | 2019-03-06 | 2019-05-03 | 马永胜 | A kind of concrete pump-feed agent |
| CN110451839A (en) * | 2019-08-20 | 2019-11-15 | 重庆腾治科技有限公司 | A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN113072316A (en) * | 2021-03-03 | 2021-07-06 | 中国矿业大学(北京) | Chlorine-free concrete antifreezing agent and preparation method and application thereof |
| CN113233815A (en) * | 2021-05-10 | 2021-08-10 | 北京工业大学 | Non-air-entraining type antifreeze agent suitable for cement-based material |
| CN115745484A (en) * | 2022-11-11 | 2023-03-07 | 杭州汉特建材有限公司 | Preparation process of anti-freezing recycled concrete |
| CN115745484B (en) * | 2022-11-11 | 2023-12-01 | 杭州汉特建材有限公司 | Preparation process of anti-freezing recycled concrete |
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Application publication date: 20120627 |