CN107573898B - Antifreezing material with controllable slow-release rate applied to concrete pavement and preparation method thereof - Google Patents
Antifreezing material with controllable slow-release rate applied to concrete pavement and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a controllable slow-release-rate anti-freezing material applied to a concrete pavement and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing the ice inhibiting component and the rust inhibitor in proportion, granulating, adding the crosslinked polymer material into the salt particles under the heating condition, stirring, spraying the waterproof coating, stirring, standing and screening to obtain the antifreeze material with controllable slow-release rate. The invention has the outstanding characteristics that the addition amount and the addition variety of the crosslinking polymer material can effectively control the structure and the thickness of the film layer, thereby effectively controlling the release rate of the ice inhibiting component and preventing the damage of the volume expansion of the ice inhibiting component to the concrete pavement.
Description
Technical Field
The invention belongs to the technical field of road pavement anti-freezing and deicing, and particularly relates to a controllable slow-release-rate anti-freezing material applied to a concrete road pavement and a preparation method thereof.
Background
Domestic and foreign investigation shows that the condition of the road surface is an important factor influencing road traffic. In cold winter, many highways and urban roads are often subjected to the hazards of ice and snow. On the ice and snow road surface, the vehicle is very easy to skid and deviate, the braking distance is also obviously prolonged, the stability and the safety of the vehicle operation are seriously influenced, and the traffic accident rate is multiplied. Due to the existence of the road icing phenomenon, the road traffic safety level is seriously reduced, the traffic capacity of a road network is reduced, even the traffic network is closed in serious conditions, the traffic transportation is paralyzed, the inconvenience is brought to the passenger and cargo transportation, and the huge economic loss is also caused to related units. In the period of rapid development of highway network construction and rapid increase of transportation vehicles in China, in order to ensure the smoothness of roads and the driving safety and avoid traffic accidents, the research on measures for preventing snow and removing snow of the roads to ensure the smoothness and the safety of snowfall weather in winter is the most important of the work of transportation departments, and particularly effective measures for preventing snow and removing snow are adopted in important occasions such as expressways, airports and the like, so that the method has very important economic benefits and social significance.
At present, the common deicing modes of airport concrete pavements mainly comprise methods of spreading snow-melting agent, strong blowing cold air, strong blowing hot air, mechanical shoveling and cleaning and the like. Compared with the passive snow removal mode, the anti-freezing material capable of removing snow actively has natural advantages, and when the anti-freezing material is paved on a road surface, the ice-suppressing component contained in the anti-freezing material can be released slowly in rainy and snowy days, so that the freezing point of the road surface is lowered, and the ice on the road surface is prevented or slowed down. The technology has the characteristics of one-time pavement, long-term effectiveness and low maintenance cost, and is widely applied to developed areas such as Europe, Japan and the like. However, the release rate of the deicing component in the drought rainy region and the humid rainy region of the existing product is the same. The ice inhibiting components in partial areas are not fully released, and the ice removing effect is not obvious. Moreover, the methods used at present cause considerable damage to the concrete pavement. Research shows that the hot air deicing causes serious damage to the internal structure of the concrete due to severe impact; on the other hand, when a snow-melting agent, particularly a urea snow-melting agent, is spread, the corrosive damage to the concrete surface layer is very significant. At present, the concrete is more freshly used in the field of concrete snow melting and deicing due to the strong corrosivity of the salt.
In view of the above situation, it is of great significance to develop an anti-freezing material which can play a role of slowly releasing ice in ice and snow weather and can not seriously damage a concrete structure.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides the antifreezing material with controllable slow release rate, which is applied to the concrete pavement. The antifreeze material with controllable slow release rate takes an ice inhibiting material and a rust inhibitor as core materials, takes a cross-linking type high polymer material and a waterproof coating as membrane materials, and is coated with the membrane materials to form a granular multilayer composite material. The composite material comprises, by weight, 74-89% of an ice inhibiting material, 0.5-1% of a rust inhibitor, 5-15% of a cross-linked polymer material and 5-10% of a waterproof coating. The cross-linked polymer material used as the slow-release shell can effectively control the release rate of the ice-suppressing component, and can form a buffer area between concrete and an ice surface due to the higher toughness of the cross-linked polymer material relative to a concrete structure, so that the damage of icing expansion to the concrete is effectively reduced.
Wherein the ice inhibiting material is one or a mixture of more than two of sodium chloride, calcium chloride, magnesium chloride, sodium formate, potassium formate, sodium acetate, potassium acetate and calcium magnesium acetate.
The rust inhibitor comprises the following components in percentage by weight: 10-20% of zinc dihydrogen phosphate, 20-30% of sodium tungstate, 15-30% of thiourea, 5-10% of tetraethylenepentamine and the balance of sodium dodecyl benzene sulfonate.
The cross-linked polymer material is: one or a mixture of more than two of epoxy resin, phenolic resin and acrylic resin.
The waterproof coating comprises the following components in percentage by weight: 40-50% of talcum powder, 40-50% of calcium carbonate and the balance of hydroxypropyl methyl cellulose.
The selected talcum powder is white powder, and the passing rate of a 0.1mm square-hole sieve is more than 90%.
The selected calcium carbonate is white powder, and the passing rate of a 0.1mm square-hole sieve is more than 90 percent.
The hydroxypropyl methyl cellulose is cream yellow powder, and the passing rate of a 0.1mm square-hole sieve is more than 90%.
In the invention, the grain size of the antifreeze material grains with controllable slow release rate is 0.5-4 mm.
The invention also provides a preparation method of the antifreezing material with controllable slow-release rate, which is applied to the concrete pavement, and the concrete steps are as follows:
(1) firstly, crushing an ice inhibiting material and a rust inhibitor, mixing, and granulating to obtain core material particles;
(2) stirring the core material particles obtained in the step (1) under a hot air blowing condition, heating the core material to 50-80 ℃, adding 1/2 cross-linked polymer material, stirring for 5-10 minutes, adding the waterproof coating under a hot air blowing condition, stirring for 5-10 minutes, adding the rest 1/2 cross-linked polymer material, and continuously stirring for 5-10 minutes to obtain coated particles;
(3) and (3) standing the coated particles obtained in the step (2) for 1 hour, and screening to obtain the antifreezing material with controllable slow release rate, which is applied to the concrete pavement.
The application method of the antifreeze material in the concrete pavement comprises the following steps:
the process of doping the antifreeze material particles with controllable slow release rate into the concrete pavement is approximately as follows: in the process of preparing paving concrete, the antifreeze material particles with controllable slow release rate are added, and the sequence of adding the antifreeze material particles into the mixing cylinder is coarse material, fine material and cement. The addition amount of the antifreeze material particles accounts for 3-5% of the total weight of the mineral aggregate. And finally, normally paving the concrete pavement doped with the anti-freezing material.
The working principle of the antifreeze material with controllable slow release rate
The anti-freezing material is added into the concrete mixture, and by utilizing the gap and capillary principle of the road surface, when the ambient temperature and humidity of the atmosphere are different from the depths of the road surface layer and the road surface layer, and the road surface is subjected to various factors such as compression, vibration, abrasion and the like, the ice-suppressing component can be extracted and migrated to the road surface layer from different depths very slowly and released, so that the ice-snow on the road surface has the effect similar to salt chemistry to prevent or delay the icing of the road surface. Because the crosslinked polymer material can form a compact network structure after being cured, the ice inhibition component coated by the material can slowly permeate the network structure in the crosslinked polymer to achieve the effect of slow release. The thickness of the film material can be directly influenced by changing the adding amount and adding type of the cross-linking polymer, the film materials with different thicknesses can play a role in slow release, and the release rate of the ice melting component can be controlled, so that the effect of controllable slow release is achieved. In addition, concrete is typically physically damaged by freezing and expanding rain in winter. Due to the high toughness of the crosslinking polymer, a buffer layer is formed between concrete and ice blocks, so that the salt freezing damage of the concrete structure caused by freezing expansion is effectively reduced.
According to the invention, the high-efficiency rust inhibitor is added, and the antifreeze material is measured according to the requirement of GB/T18175 'rotating hanging piece method for measuring corrosion inhibition performance of water treatment agent', so that the high-efficiency rust inhibitor can form a compact adsorption film on the metal surface, and effectively inhibits ions from corroding the metal surface. And the rust inhibitor has no toxicity per se, is environment-friendly and has little use amount.
The invention has the beneficial effects that: the product is an active anti-freezing material, has quick anti-freezing response and can ensure the safe and smooth road to the maximum extent. The addition of the rust inhibitor can minimize damage to infrastructure and vehicles by the product. The waterproof coating eliminates the water absorption phenomenon of part of the core material in the preparation process, and meanwhile, the waterproof coating also has a certain hydrophobic characteristic and can increase the slow release property of the anti-freezing material to a certain extent. After the waterproof coating is wrapped by the high-toughness cross-linked polymer material, a compact water-resisting film is formed on the surface of the core material through curing, water molecules can be effectively prevented from entering the core material, the slow release effect is finally achieved, and meanwhile damage of freezing volume expansion to a concrete physical structure can be effectively reduced. The antifreeze material with controllable slow release rate can adapt to the environment of different areas, for example, areas with large rainfall in summer and higher temperature in winter can select the antifreeze material with slower release rate; and areas with low rainfall in summer and low temperature in winter can be selected to be anti-freezing materials with fast release rate.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1:
weighing 80g of sodium chloride and 4g of calcium chloride;
1g of rust inhibitor: 0.2g of zinc dihydrogen phosphate, 0.25g of sodium tungstate, 0.25g of thiourea, 0.1g of tetraethylenepentamine and 0.2g of sodium dodecyl benzene sulfonate;
5g of crosslinking type high polymer material: wherein, 2g of epoxy resin and 3g of phenolic resin;
10g of waterproof coating: 4g of talcum powder, 4g of calcium carbonate and 2g of hydroxypropyl methyl cellulose;
the preparation method comprises the following specific steps:
(1) firstly, putting sodium chloride, calcium chloride and a rust inhibitor into a flour mill together, crushing, mixing, spraying a certain amount of water, and granulating by using granulation equipment to obtain core material particles;
(2) stirring the core material particles obtained in the step (1) under the condition of hot blast until the core material is heated to 50 ℃, adding 2.5g of cross-linked polymer material, stirring for 5 minutes, then adding a waterproof coating (talcum powder, calcium carbonate and hydroxypropyl methyl cellulose) under the condition of hot blast, stirring for 5 minutes, adding the rest 2.5g of cross-linked polymer material, and continuously stirring for 5 minutes to obtain the coated particles.
(3) And (3) standing the coated particles obtained in the step (2) for 1 hour, and screening to obtain the antifreeze material with the particle size of 2-4mm and controllable slow release rate.
Example 2
75g of sodium chloride and 4g of calcium chloride are weighed.
1g of rust inhibitor: wherein, 0.2g of zinc dihydrogen phosphate, 0.25g of sodium tungstate, 0.25g of thiourea, 0.1g of tetraethylenepentamine and 0.2g of sodium dodecyl benzene sulfonate.
10g of crosslinked polymer material: the weight percentage of the phenolic resin is 5g, and the weight percentage of the acrylic resin is 5 g.
10g of waterproof coating: wherein, 4g of talcum powder, 4g of calcium carbonate and 2g of hydroxypropyl methyl cellulose.
The preparation is as in example 1.
Example 3
70g of sodium chloride and 4g of calcium chloride are weighed.
1g of rust inhibitor: wherein, 0.2g of zinc dihydrogen phosphate, 0.25g of sodium tungstate, 0.25g of thiourea, 0.1g of tetraethylenepentamine and 0.2g of sodium dodecyl benzene sulfonate.
15g of crosslinking type polymer material: wherein, the epoxy resin accounts for 7g, and the acrylic resin accounts for 8 g.
10g of waterproof coating: wherein, 4g of talcum powder, 4g of calcium carbonate and 2g of hydroxypropyl methyl cellulose.
The preparation is as in example 1.
Comparative example 1
80g of sodium chloride and 4g of calcium chloride are weighed.
5g of crosslinking type high polymer material: wherein, 2g of epoxy resin and 3g of phenolic resin;
10g of waterproof coating: wherein, 4g of talcum powder, 4g of calcium carbonate and 2g of hydroxypropyl methyl cellulose.
The preparation process comprises the following steps:
(1) firstly, putting sodium chloride and calcium chloride into a flour mill together, crushing, mixing, spraying a certain amount of water, and granulating by using granulation equipment to obtain core material particles;
(2) stirring the core material particles obtained in the step (1) under the condition of hot blast until the core material is heated to 50 ℃, adding 2.5g of cross-linked polymer material, stirring for 5 minutes, then adding a waterproof coating (talcum powder, calcium carbonate and hydroxypropyl methyl cellulose) under the condition of hot blast, stirring for 5 minutes, adding the rest 2.5g of cross-linked polymer material, and continuously stirring for 5 minutes to obtain the coated particles.
(3) And (3) standing the coated particles obtained in the step (2) for 1 hour, and screening to obtain the antifreeze material with the particle size of 2-4mm and controllable slow release rate.
Comparative example 2
80g of sodium chloride and 4g of calcium chloride are weighed.
1g of rust inhibitor: 0.2g of zinc dihydrogen phosphate, 0.25g of sodium tungstate, 0.25g of thiourea, 0.1g of tetraethylenepentamine and 0.2g of sodium dodecyl benzene sulfonate;
10g of waterproof coating: wherein, 4g of talcum powder, 4g of calcium carbonate and 2g of hydroxypropyl methyl cellulose.
The preparation process comprises the following steps:
(1) firstly, putting sodium chloride, calcium chloride and a rust inhibitor into a flour mill together, crushing, mixing, spraying a certain amount of water, and granulating by using granulation equipment to obtain core material particles;
(2) stirring the core material particles obtained in the step (1) under the condition of hot blast until the core material is heated to 50 ℃, adding a waterproof coating (talcum powder, calcium carbonate and hydroxypropyl methyl cellulose) and stirring for 5 minutes to obtain the coated particles. The waterproof coating was found not to adhere effectively to the particle surface during the preparation.
Comparative example 3
80g of sodium chloride and 4g of calcium chloride are weighed.
1g of rust inhibitor: 0.2g of zinc dihydrogen phosphate, 0.25g of sodium tungstate, 0.25g of thiourea, 0.1g of tetraethylenepentamine and 0.2g of sodium dodecyl benzene sulfonate;
5g of crosslinking type high polymer material: wherein, 2g of epoxy resin and 3g of phenolic resin;
the preparation process comprises the following steps:
(1) firstly, putting sodium chloride, calcium chloride and a rust inhibitor into a flour mill together, crushing, mixing, spraying a certain amount of water, and granulating by using granulation equipment to obtain core material particles;
(2) stirring the core material particles obtained in the step (1) under the condition of hot blast until the core material is heated to 50 ℃, adding 2.5g of cross-linked polymer material, stirring for 5 minutes, adding the rest 2.5g of cross-linked polymer material, and continuously stirring for 5 minutes to obtain the coated particles.
(3) And (3) standing the coated particles obtained in the step (2) for 1 hour, and screening to obtain the antifreeze material with the particle size of 2-4mm and controllable slow release rate.
Experiment 1 corrosion rate of the antifreeze material with controllable slow release rate of the invention to carbon steel:
according to the test methods and conditions of GB/T18175-2000 "determination of corrosion inhibition performance of water treatment agent", carbon steel corrosion tests were carried out on the antifreeze materials with controllable slow-release rates prepared in the above examples 1, 2 and 3 and comparative example 4, pure water, pure components of sodium chloride, calcium chloride, magnesium chloride, sodium formate, potassium formate, sodium acetate, potassium acetate and calcium magnesium acetate, respectively, and the comparison results are shown in Table 1:
TABLE 1 comparative results of corrosion tests of antifreeze materials on carbon steel
| Sample (I) | Average corrosion inhibition rate mm/a |
| Pure water | 0.0589 |
| Sodium chloride | 0.3911 |
| Calcium chloride | 0.2227 |
| Magnesium chloride | 0.4592 |
| Urea | 0.5118 |
| Potassium acetate | 0.0689 |
| Calcium magnesium acetate | 0.0758 |
| Example 1 | 0.0456 |
| Example 2 | 0.0458 |
| Example 3 | 0.0317 |
| Comparative example 1 | 0.4236 |
Table 1 shows that the corrosion resistance of the antifreeze agent is obviously reduced by adding the rust inhibitor, and the test result can reach the national standard GBT 23851-. .
Experiment 2 hardness test of antifreeze material with controllable slow release rate
An experimental instrument: particle strength tester (made by Japan rattan original)
The testing steps are as follows: from the samples of examples 1, 2, 3 and uncoated antifreeze pellets, 10 pellets (2.5-3 mm in size) were randomly taken and measured as described above. And (4) discarding a minimum value and a maximum value, and taking the average value of the rest hardness values as the hardness of the anti-freezing deicing material. The results are shown in Table 2:
TABLE 2 hardness test results for antifreeze materials
| Sample (I) | hardness/N |
| Example 1 | 47.36 |
| Example 2 | 49.72 |
| Example 3 | 46.32 |
| Comparative example 1 | 43.17 |
| Comparative example 2 | 20.16 |
| Comparative example 3 | 46.86 |
| Granulation of chloride mixture | 21.39 |
| Chloride plus corrosion inhibitor granulation | 19.54 |
The results in table 2 show that the addition of the rust inhibitor has a certain limitation on the hardness of the chloride granules, but the coating of the film material can greatly increase the hardness of the granules, and particularly, the addition of the cross-linked polymer material greatly increases the hardness of the granules. The improvement of the particle hardness reduces the abrasion and the breakage of the product in the transportation process, and simultaneously, the product is not broken in the mixing process with the concrete to influence the use effect of the product.
Experiment 3 film material slow release property of antifreeze material with controllable slow release rate
The granules prepared in example 1, comparative example 2 and comparative example 3 were subjected to a test for measuring sustained release in pure water. The test refers to the industry standard of HG/T3931-2007 slow and controlled release fertilizers. The test results were compared and are shown in table 3:
TABLE 3 film material sustained-release characteristic measurement test results of the anti-freezing material
The data in Table 3 show that the crosslinked polymer material alone does not exert a sustained release effect well. The pure waterproof coating cannot be effectively attached to the surface of the particle and cannot well play a hydrophobic role, and the combination of the pure waterproof coating and the pure waterproof coating can well combine hydrophobicity and slow release together to realize an excellent slow release effect.
Experiment 4 the controlled release rate antifreeze material of the invention has the slow release characteristics:
the controlled-release-rate antifreeze materials prepared in the above examples 1, 2 and 3 and the non-coated antifreeze were subjected to a test for determining the release in pure water. The test refers to the industry standard of HG/T3931-2007 slow and controlled release fertilizers. The test results were compared and are shown in table 4:
TABLE 4 test results for the determination of the Slow Release of antifreeze materials
The results in Table 4 show that an increase in the amount of coating material used can directly decrease the release rate of the core material, and thus control the thickness of the coating material can control the slow release rate of the antifreeze material.
Experiment 5 pavement deicing effect experiment of the antifreeze material with controllable slow release rate of the invention:
the antifreeze material with controllable slow release rate in the embodiment 1 of the invention is mixed into the concrete mixing material according to the mass percentage of 4 percent, and is uniformly stirred to prepare a concrete sample which is marked as a concrete sample 1; recording a test piece made of the antifreezing material which is not added with the controllable slow-release rate as a concrete test piece 2, respectively spraying water on the surface of the test piece, then placing the test piece in a low-temperature incubator at minus 10 ℃ for freezing for 12h, and displaying the test result that the concrete test piece added with the antifreezing material is not frozen and the surface of the test piece not added with the antifreezing material is frozen.
Claims (3)
1. The antifreezing material with controllable slow-release rate is used for maintaining a concrete pavement, and is characterized in that: the anti-freezing material takes an ice inhibiting material and a rust inhibitor as core materials, takes a cross-linked polymer material and a waterproof coating as membrane materials, and is coated with the membrane materials to form a granular multilayer composite material;
the antifreeze material comprises the following components in percentage by weight: 74-89% of ice inhibiting material, 0.5-1% of rust inhibitor, 5-15% of cross-linked polymer material and 5-10% of waterproof coating;
the rust inhibitor comprises the following components in percentage by weight: 10-20% of zinc dihydrogen phosphate, 20-30% of sodium tungstate, 15-30% of thiourea, 5-10% of tetraethylenepentamine and the balance of sodium dodecyl benzene sulfonate;
the cross-linked polymer material is as follows: one or a mixture of more than two of epoxy resin, phenolic resin and acrylic resin;
the waterproof coating comprises the following components in percentage by weight: 40-50% of talcum powder, 40-50% of calcium carbonate and the balance of hydroxypropyl methyl cellulose;
the preparation method of the antifreeze material with controllable slow release rate comprises the following specific steps:
(1) firstly, crushing an ice inhibiting material and a rust inhibitor, mixing, and granulating to obtain core material particles;
(2) stirring the core material particles obtained in the step (1) under a hot air blowing condition, heating the core material to 50-80 ℃, adding 1/2 cross-linked polymer material, stirring for 5-10 minutes, adding the waterproof coating under a hot air blowing condition, stirring for 5-10 minutes, adding the rest 1/2 cross-linked polymer material, and continuously stirring for 5-10 minutes to obtain coated particles;
(3) and (3) standing the coated particles obtained in the step (2) for 1 hour, and screening to obtain the antifreeze material with controllable slow release rate.
2. Use of a controlled release rate antifreeze material according to claim 1 for the maintenance of concrete pavements, wherein: the ice inhibiting material is as follows: one or more of sodium chloride, calcium chloride, magnesium chloride, urea, potassium acetate and calcium magnesium acetate.
3. Use of a controlled release rate antifreeze material according to claim 1 for the maintenance of concrete pavements, wherein: the maintenance and use method of the anti-freezing material for the concrete pavement comprises the following steps:
in the process of preparing paving concrete, antifreeze material particles with controllable slow release rate are added into the mixing cylinder in sequence of coarse material, fine material and cement, and finally, the antifreeze material particles are added, wherein the addition amount of the antifreeze material particles accounts for 3-5% of the total weight of the mineral aggregate, and the concrete pavement doped with the antifreeze material is laid normally.
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| CN108531081B (en) * | 2018-04-19 | 2020-12-18 | 中盐金坛盐化有限责任公司 | Slow-release environment-friendly anti-freezing coating applied to asphalt pavement and preparation method thereof |
| CN109486225A (en) * | 2018-11-28 | 2019-03-19 | 常州履信新材料科技有限公司 | The freeze proof material of powder-type, the moisture-proof membrane material of sustained release for bituminous pavement and preparation method thereof |
| CN109943177B (en) * | 2019-03-21 | 2021-06-15 | 华北水利水电大学 | Environment-friendly efficient ice melting coating material and preparation method and application thereof |
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| CN104774592A (en) * | 2015-04-10 | 2015-07-15 | 常州履信新材料科技有限公司 | Slow-release antifreezing material for asphalt pavements and preparation method thereof |
| CN104829157A (en) * | 2015-04-10 | 2015-08-12 | 常州履信新材料科技有限公司 | Temperature-sensitive antifreezing material for asphalt pavement and preparation method thereof |
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| CN104829157A (en) * | 2015-04-10 | 2015-08-12 | 常州履信新材料科技有限公司 | Temperature-sensitive antifreezing material for asphalt pavement and preparation method thereof |
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