CN107540336B - Application of modified sulfur in improving compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete and sulfur mortar - Google Patents
Application of modified sulfur in improving compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete and sulfur mortar Download PDFInfo
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Abstract
The invention discloses application of modified sulfur in improving the compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete or sulfur mortar. The modified sulfur is formed by modifying sulfur with a modifier dicyclopentadiene; the modified sulfur concrete comprises the following raw materials in percentage by mass: 15 to 20 percent of modified sulfur, 12 to 27 percent of filler, 50 to 60 percent of stone and 18 to 28 percent of sand; the modified sulfur mortar comprises the following raw materials in parts by weight: 20 to 37 percent of modified sulfur, 15 to 48 percent of filler and 50 to 75 percent of sand. Compared with silicate concrete, the modified sulfur concrete and the modified sulfur mortar have excellent compressive strength, acid corrosion resistance and/or permeability resistance, do not need water or maintenance in the preparation process, have extremely high condensation speed, and can be cast in a freezing environment; the used cementing material sulfur is a petroleum byproduct, and the material can be completely recycled.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to application of modified sulfur in improving compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete and sulfur mortar.
Background
The sulfur concrete is a thermoplastic building material which uses sulfur as a cementing material, and after the filler and the aggregate are mixed by melting the sulfur, the mixture is cooled along with the solidification of the sulfur, and the strength is rapidly obtained. Because the sulfur concrete has the characteristics of high strength, low permeability, acid and alkali resistance, fatigue resistance, quick setting and the like, the sulfur concrete is widely applied to the construction of infrastructures, such as civil use, industry, transportation and the like, all over the world.
The corrosion resistance and the permeability resistance of the common silicate concrete are often poor, such as the acid corrosion resistance is very poor. While in urban and industrial production areas, acidic environments are prevalent. The annual costs of acid-corroded sewer pipe repair in the united states are reported to amount to $ 250 billion, even higher than the annual budget costs of constructing new sewer pipes. With the increasing frequency of human transformation natural activities and the acceleration of modernization processes, the environment is increasingly polluted and the distribution of corrosive environment is also increasingly wide. The sulfur concrete has excellent corrosion resistance and permeability resistance and good durability.
The sulfur concrete also has the performance which is not possessed by a plurality of silicate concrete, can make up the defects of the application of the sulfur concrete in many aspects, and simultaneously has other excellent characteristics of the silicate concrete, so that the sulfur concrete has very potentialThe high-performance building material. Meanwhile, the sulfur concrete is a green building material prepared from petroleum byproducts and has the characteristic of recycling, and the production of Portland cement can generate a large amount of CO2So that the sulfur concrete is more in line with the scientific concept of sustainable development in the future. Therefore, the sulfur concrete can become a good substitute of silicate concrete.
Disclosure of Invention
The invention aims to provide application of modified sulfur in improving the compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete and sulfur mortar. The modified sulfur is used as a partial cementing material, so that the modified sulfur is applied to the preparation of modified sulfur concrete and modified sulfur mortar, and the compressive strength, acid and alkali corrosion resistance and the like of the modified sulfur concrete and the modified sulfur mortar are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of the modified sulfur in improving the compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete or sulfur mortar is characterized in that the modified sulfur is formed by modifying sulfur with a modifier dicyclopentadiene, and the modifier accounts for 1-5% of the sulfur by mass; the modified sulfur concrete comprises the following raw materials in percentage by mass: 15 to 20 percent of modified sulfur, 12 to 27 percent of filler, 50 to 60 percent of stone and 18 to 28 percent of sand; the modified sulfur mortar comprises the following raw materials in parts by weight: 20 to 37 percent of modified sulfur, 15 to 48 percent of filler and 50 to 75 percent of sand.
Preferably, the modifier accounts for 3% of the sulfur by mass, and the modified sulfur concrete comprises the following raw materials by mass: 15 percent of modified sulfur, 13.5 percent of filler, 51 percent of stone and 20.5 percent of sand.
Preferably, the modifier accounts for 3% of the sulfur by mass, and the modified sulfur mortar comprises the following raw materials by mass: 24% of modified sulfur, 21.6% of filler and 54.4% of sand.
Preferably, the filler is one or more of quartz powder, fly ash, mineral powder and cement micro powder, and the specific surface area of the filler is not less than 300m2/kg。
Preferably, the sand is one or more of river sand, quartz sand and machine-made sand.
The modified sulfur concrete is prepared by the following steps:
s1, heating the sulfur at the melting temperature, and adding a modifier for reaction to obtain modified sulfur;
s2, uniformly mixing the modified sulfur and the corresponding preheated filler at the melting temperature;
s3, adding preheated stone and sand into the mixture obtained in the step S2 at the melting temperature, uniformly stirring, and then pouring;
wherein the melting temperature in the steps S1-S3 is 130-150 ℃, and the reaction time in the step S1 is 1-3 h;
preferably, the melting temperature in steps S1-S3 is 140 ℃, and the reaction time in step S1 is 2 h.
The modified sulfur mortar is prepared by the following steps:
s1, heating the sulfur at the melting temperature, and adding a modifier for reaction to obtain modified sulfur;
s2, uniformly mixing the modified sulfur and the corresponding preheated filler at the melting temperature;
s3, adding preheated sand into the mixture obtained in the step S2 at the melting temperature, uniformly stirring, and then pouring;
wherein the melting temperature in the steps S1-S3 is 130-150 ℃, and the reaction time in the step S4 is 1-3 h.
Preferably, the melting temperature in steps S1-S3 is 140 ℃, and the reaction time in step S4 is 2 h.
Compared with the prior art, the invention has the advantages that:
1. the modified sulfur concrete of the invention is obviously superior to the common silicate concrete in the aspects of mechanical properties including compressive strength, rupture strength, fatigue life and the like, and the compressive strength exceeds 80 MPa; the compressive strength of the high-strength modified sulfur mortar exceeds 60 MPa;
2. compared with silicate concrete, the modified sulfur concrete and the modified sulfur mortar have excellent acid corrosion resistance and permeability resistance, and almost have excellent resistance to all acidic and salt solution environments;
3. the modified sulfur concrete and the modified sulfur mortar do not need to be maintained, the setting speed is extremely high, the final strength can reach 80 percent within a few hours, and the final strength can reach more than 90 percent within one day;
4. the modified sulfur concrete and the modified sulfur mortar can be poured in a freezing environment;
5. the modified sulfur concrete and the modified sulfur mortar do not need water during preparation, and are an excellent substitute for silicate concrete in water-deficient and arid areas;
6. the modified sulfur concrete and the modified sulfur mortar are environment-friendly, and the petroleum byproduct is used as a cementing material, so that the material can be completely recycled after being integrally melted.
The modified sulfur concrete and the modified sulfur mortar have the advantages, have the advantages of strong plasticity, good integrity, convenient material taking, low manufacturing cost, convenient construction and the like of silicate concrete, can be applied to superstructure and foundation structures of buildings, and are also suitable for environments requiring high corrosion resistance and permeation resistance, such as municipal sewage treatment facilities, industrial ground, marine concrete and the like, and have good social and economic effects.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the high-strength modified sulfur concrete comprises the following steps of preparing 15% of sulfur by mass, wherein a modifier DCPD accounts for 3% of the sulfur by mass, cement accounts for 13.5% of the total mass, river sand accounts for 20.5% of the total mass, and granite coarse aggregate accounts for 51% of the total mass.
The method comprises the following steps: at 140 ℃, sulfur is melted, and then 3 percent of DCPD by mass is weighed and added for reaction for 2 hours.
Step two: uniformly combining the modified sulfur obtained in the step one with the corresponding preheated cement filler at 140 ℃.
Step three: and (3) adding river sand and granite which are preheated in advance into the mixture obtained in the step two at 140 ℃, uniformly stirring, pouring into a preheated cast iron test mold after vibrating for 60 seconds, and removing the mold after cooling for 1d at normal temperature.
The 3d compressive strength of the modified sulfur concrete test piece reaches 82.5MPa, and the mixture has good fluidity.
Example 2
The preparation method of the high-strength modified sulfur mortar comprises the following steps of preparing 24% of sulfur by mass, wherein a modifier DCPD accounts for 3% of the sulfur by mass, cement accounts for 21.6% of the total mass, and river sand accounts for 54.4% of the total mass.
The method comprises the following steps: at 140 ℃, sulfur is melted, and then 3 percent of DCPD by mass is weighed and added for reaction for 2 hours.
Step two: uniformly combining the modified sulfur obtained in the step one with the corresponding preheated cement filler at 140 ℃.
Step three: and (3) adding river sand preheated in advance into the mixture obtained in the step two at 140 ℃, uniformly stirring, pouring into a preheated cast iron test mold after vibrating for 60 seconds, and removing the mold after cooling for 1d at normal temperature.
The 3d compressive strength of the modified sulfur mortar test piece reaches 62.3MPa, and the flexural strength reaches 11.9 MPa.
Example 3
The experiment is the research of the permeability of the modified sulfur concrete and the modified sulfur mortar. The method is characterized in that the chloride ion permeability resistance of common concrete, modified sulfur concrete and modified sulfur mortar is comprehensively evaluated by adopting an ASTM C1202 standard test method, namely an electric flux method, the size of a test piece of the method is phi 100mm multiplied by 50mm, wherein the silicate concrete is cured to the age of 28d under the standard condition, the modified sulfur concrete is taken out after being cured for 1d at room temperature, the modified sulfur concrete is placed in a vacuum water saturation device, firstly vacuumized for 3h, then added with water and pumped for 1h, and then continuously soaked for 18 h. And (3) respectively filling a NaCl solution with the concentration of 3% and a NaOH solution with the concentration of 0.3mol/L into the cathode and the anode of the test piece, applying a direct current voltage of 60V to the axial direction of the concrete test piece, and recording the electric quantity Q value passing through the test piece within 6h so as to measure the compactness degree and the chloride ion permeation resistance of the concrete. The electric flux of the modified sulfur mortar and the modified sulfur concrete in the age of 1d, 3d, 7d and 28d in room temperature curing is measured according to the ASTM C1202 standard method, and then compared with the electric flux value of the silicate concrete (C50 and C100) in the age of 28d in standard curing to evaluate the chloride ion penetration resistance of each group of test pieces. The lower the Q value of the electric flux, the better the resistance of the test piece to the penetration of chloride ions.
The experimental results are shown in tables 1 and 2.
TABLE 1 electric flux measurements for modified sulphur mortar (SPM) and modified sulphur concrete (SPC)
Note: g1 in the table refers to 5mm-10mm melon and rice stone produced in Huizhou stone farm; g2 refers to granite crushed stone of 10mm-18mm produced in Huizhou stone yard.
TABLE 2 electric flux measurements for C50 and C100 silicate concrete
As can be seen from tables 1 and 2, the modified sulfur mortar and the modified sulfur concrete have much better chlorine ion penetration resistance than silicate concrete. Under the experimental condition, the 6h electric flux of the modified sulfur mortar is 0.011 time of that of C50 silicate concrete and 0.315 time of that of C100 silicate concrete; the 6h electric flux of the modified sulfur concrete is 0.018 times that of C50 silicate concrete and 0.507 times that of C100 silicate concrete. The modified sulfur mortar and the modified sulfur concrete have fewer pores, and the modified sulfur matrix has extremely high hydrophobicity, so that the whole material is difficult to permeate water after the aggregate particles are coated. The experimental results show that the C50 silicate concrete has poor permeation resistance, and the C100 silicate concrete has good permeation resistance; the anti-permeability performance of the modified sulfur concrete and the modified sulfur mortar is far better than that of C50 medium-strength silicate concrete and C100 ultrahigh-strength silicate concrete.
Example 4
The experiment is a study on the acid and alkali corrosion resistance of the modified sulfur concrete and the modified sulfur mortar. And testing the mass loss and the strength loss of the modified sulfur concrete, the modified sulfur mortar and the silicate concrete test piece after being respectively soaked for 7 days in acid-base solutions with high concentration by using acid-base solutions such as sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide and the like so as to characterize the acid-base corrosion resistance of the modified sulfur concrete, the modified sulfur mortar and the silicate concrete test piece.
In order to research the difference of the influence of different corrosive substances on the test piece, the experiment is realized by controlling the molar concentration of different corrosive liquids. Sulfuric acid, hydrochloric acid, phosphoric acid and sodium hydroxide solution with the mole fraction of 8mol/L are adopted as soaking erosion liquid. All test pieces used were cubes of 7cm by 7 cm. A1000 mL beaker is independently used as a container for each test piece, and the beaker is covered with a preservative film for preservation so as to prevent the corrosion liquid from volatilizing and absorbing water.
The sulfuric acid, hydrochloric acid, phosphoric acid and sodium hydroxide used in the test are analytical reagents:
the mass fraction of analytically pure concentrated sulfuric acid is 98 percent, the density is 1.84g/mL, and H is2SO4Has a molecular weight of 98, the molar concentrations used are: 1.84 × 1000 × 0.98/98=18.4 mol/L.
The analytically pure hydrochloric acid has a mass fraction of between 36% and 38%, a density of 1.19g/mL, a molecular weight of HCl of 36.5, and the molar concentrations used are: 1000 × 0.37 × 1.19/36.5 =12.063 mol/L.
The analytically pure phosphoric acid solution has a phosphoric acid content of not less than 85%, the density of phosphoric acid is 1.69 and the molecular weight is 98 when the concentration is calculated by 85%, and the molar concentration used by the analytically pure phosphoric acid solution is as follows: 1000 × 1.69 × 85%/98=14.7 mol/L.
The sodium hydroxide solution is prepared by using an analytical reagent, and the NaOH content is more than 98 percent.
Preparing 8mol/L of erosion liquid of corresponding acid and alkali according to the molar concentration. After preparing each erosion liquid, pouring 500mL of erosion liquid into each 1000mL beaker, then putting the corresponding test piece, sealing the test piece in an environment at 20 ℃ by using a preservative film, and not adjusting the concentration of the solution after preparing the erosion liquid. The modified sulfur concrete and the modified sulfur mortar are cured for 3d at room temperature, and the silicate concrete test piece is cured for 7d in a standard manner and then starts to be subjected to a soaking erosion test. The specific proportions of modified sulfur concrete (SPC), modified sulfur mortar (SPM) and C50 silicate concrete (PCC) are shown in Table 3:
TABLE 3 SPC, SPM, PCC ratios
Note: g1 in the table refers to 5mm-10mm melon and rice stone produced in Huizhou stone farm; g2 refers to granite crushed stone of 10mm-18mm produced in Huizhou stone yard.
The results are shown in tables 4 and 5.
TABLE 4 Mass loss after soaking SPC, SPM, PCC in different solutions for 7 days
TABLE 5 Strength loss after soaking SPC, SPM, PCC in different solutions for 7 days
The results of the mass loss and the strength loss after the modified sulfur concrete, the modified sulfur mortar and the silicate concrete are respectively soaked in sulfuric acid, phosphoric acid, hydrochloric acid and sodium hydroxide solution for 7 days can be known as follows:
(1) under the experimental condition, in an 8mol/L sulfuric acid, hydrochloric acid and phosphoric acid corrosion environment, the quality of the modified sulfur concrete and the modified sulfur mortar is hardly influenced, the strength loss is small and is only 3.9% at most; under the corrosion of 8mol/L sodium hydroxide, the modified sulfur concrete and the modified sulfur mortar have certain loss of quality, but the loss of quality in a short period is small, and the loss of strength is also small, and the highest loss is 6.7 percent.
(2) Under the test condition, in an 8mol/L sulfuric acid and hydrochloric acid corrosion environment, the corrosion of silicate concrete is serious, and the mechanical property is greatly reduced to 56.4%; less performance degradation under short-term phosphoric acid erosion; under the short-term corrosion of 8mol/L sodium hydroxide solution, the quality and the appearance of the solution are almost unchanged, but the mechanical property is greatly reduced by 24.5 percent.
(3) Under the test condition, the corrosion deterioration effect of the hydrochloric acid on the modified sulfur concrete, the modified sulfur mortar and the silicate concrete is stronger than that of sulfuric acid and phosphoric acid solution with the same concentration, which is probably caused by the fact that the leaching rate of chlorine salt by the concrete or the mortar is larger than that of sulfate and phosphate.
(4) The acid corrosion resistance of the modified sulfur concrete and the modified sulfur mortar is far better than that of silicate concrete, and the alkali corrosion resistance of the modified sulfur concrete and the modified sulfur mortar is also better than that of silicate concrete in terms of short-term strength.
Comparative example 1
The two modifiers DCPD and Styrene in the examples are respectively used, and the modification effect of the modifiers on the sulfur mortar when the modifiers are singly mixed is studied. All the mortar samples adopt the mixture ratio of 70 percent river sand and 30 percent sulfur, the DCPD is controlled to respectively replace 1 percent, 3 percent and 5 percent of the mass of the sulfur, and the Styrene respectively replaces 1 percent, 5 percent and 10 percent of the mass of the sulfur. The test is carried out by uniformly adopting a standard test piece of 4cm multiplied by 16cm, curing the prepared test piece to 1d, 3d, 7d and 28d respectively at room temperature, and carrying out the flexural strength test and the compressive strength test. The sulphur mortar preparation protocol is according to the American society for testing and materials ASTM C287-98 standard.
The effect of the DCPD and Styrene content on the performance of the sulfur mortar is shown in tables 6 and 7.
TABLE 6 Effect of DCPD content on Sulfur mortar Performance
TABLE 7 Effect of Styrene content on Sulfur mortar Performance
As can be seen from tables 6 and 7, the compressive strength and the flexural strength of the pure sulfur mortar decrease with age, the compressive strength and the flexural strength of the pure sulfur mortar are respectively 20.1MPa and 4.1MPa for 28d, and the compressive strength and the flexural strength of the pure sulfur mortar decrease by 20.9% and 28.7% for 28d and 1d, respectively. When the DCPD mixing amount is 3%, the 28d compressive strength and the flexural strength of the sulfur mortar are respectively 51.7MPa and 11.9MPa, which are respectively improved by 157.2% and 190.2% compared with the pure sulfur mortar. The compression strength and the rupture strength of the sulfur mortar doped with the DCPD are not changed greatly along with time, and the maximum improvement range of the compression strength relative to a pure sulfur group at 1d is 98.4 percent. The compression strength and the breaking strength of the DCPD sulfur mortar can reach more than 80 percent of 28d within 1 d. The compressive strength of the sulfur mortar doped with Styrene has a remarkable increasing trend along with the increase of age at 1 d-7 d, and the overall stable situation appears at 7 d-28 d. When the addition amount of Styrene is more than 1%, the early compressive strength of the sulfur mortar is weakened along with the increase of the addition amount, and when the addition amount of Styrene is 1%, the compressive strength of the sulfur mortar shows the best compressive performance at any age, and is improved by 75% compared with a pure sulfur group at the age of 28 d. The bending strength of the sulfur mortar is improved best by 10% of Styrene group, and the bending strength of the sulfur mortar is improved by 148.7% by 28d compared with that of pure sulfur group. Comparing two sulfur modifiers DCPD and Styrene can find that: at 28 days, the best improvement effect of the DCPD on the compressive strength and the breaking strength of the sulfur mortar is respectively 2 times and 1.3 times of the best improvement effect of the Styrene. The DCPD has more stable and higher promotion effect than Styrene on the compression resistance and the fracture resistance of the sulfur mortar.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The application of the modified sulfur in improving the compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete or sulfur mortar is characterized in that the modified sulfur is formed by modifying sulfur with a modifier dicyclopentadiene, and the modifier accounts for 3% of the sulfur by mass; the modified sulfur concrete comprises the following raw materials in percentage by mass: 15 percent of modified sulfur, 13.5 percent of filler, 51 percent of stone and 20.5 percent of sand; or the modified sulfur mortar comprises the following raw materials in percentage by mass: 24% of modified sulfur, 21.6% of filler and 54.4% of sand;
the filler is one or more of quartz powder, fly ash, mineral powder and cement micro powder, and the specific surface area of the filler is not less than 300m2/kg；
The sand is one or more of river sand, quartz sand and machine-made sand;
the modified sulfur concrete is prepared by the following steps:
s1, heating sulfur at a melting temperature, and adding a modifier for reaction to obtain modified sulfur;
s2, uniformly mixing the modified sulfur and the corresponding preheated filler at a melting temperature;
s3, adding preheated stone and sand into the mixture obtained in the step S2 at a melting temperature, uniformly stirring, and then performing pouring operation;
wherein the melting temperature in the steps S1-S3 is 130-150 ℃, and the reaction time in the step S1 is 1-3 h.
2. The use of the modified sulfur according to claim 1 for improving the compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete or sulfur mortar, wherein the melting temperature in steps S1-S3 is 140 ℃ and the reaction time in step S1 is 2 hours.
3. The use of the modified sulphur of claim 1 for improving the compressive strength, corrosion resistance and/or permeation resistance of sulphur concrete or sulphur mortar, wherein the modified sulphur mortar is prepared by the steps of:
s1, heating sulfur at a melting temperature, and adding a modifier for reaction to obtain modified sulfur;
s2, uniformly mixing the modified sulfur and the corresponding preheated filler at a melting temperature;
s3, adding preheated sand into the mixture obtained in the step S2 at a melting temperature, uniformly stirring, and then performing pouring operation;
wherein the melting temperature in the steps S1-S3 is 130-150 ℃, and the reaction time in the step S3 is 1-3 h.
4. The use of the modified sulfur according to claim 3 for improving the compressive strength, corrosion resistance and/or permeation resistance of sulfur concrete or sulfur mortar, wherein the melting temperature in steps S1-S3 is 140 ℃ and the reaction time in step S4 is 2 hours.
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| CN109650839A (en) * | 2019-02-26 | 2019-04-19 | 中国人民解放军陆军勤务学院 | A kind of sulphur concrete and preparation method thereof of anti-distillation corrosion |
| CN111875323A (en) * | 2020-07-30 | 2020-11-03 | 内蒙古工业大学 | Coal tar modified durable sulfur concrete and preparation method thereof |
| CN113199593B (en) * | 2021-05-19 | 2022-08-05 | 暨南大学 | Process for preparing high-strength modified sulfur concrete by cold water bath vibration forming method |
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