CN107540336A - A kind of application of modified sulfur in lifting sulphur concrete and sulphur-bonded mortar compression strength, anticorrosive and/or anti-permeability performance - Google Patents
A kind of application of modified sulfur in lifting sulphur concrete and sulphur-bonded mortar compression strength, anticorrosive and/or anti-permeability performance Download PDFInfo
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Abstract
The invention discloses a kind of application of modified sulfur in lifting sulphur concrete or sulphur-bonded mortar compression strength, anticorrosive and/or anti-permeability performance.Modified sulfur is formed by the dicyclic pentylene modified sulphur of modifying agent；Wherein, modified sulfur concrete includes following raw material by mass percentage：Modified sulfur 15%~20%, filler 12%~27%, building stones 50%~60%, sand 18%~28%；Modified sulfur mortar includes following raw material according to the mass fraction：Modified sulfur 20%~37%, filler 15%~48%, sand 50%~75%.Modified sulfur concrete and modified sulfur mortar of the present invention are with respect to silicate concrete, with splendid compression strength, acidresistant property and/or permeability resistance, do not needed in preparation process water, need not conserve, rate of set is exceedingly fast, can carry out pouring operation under refrigerated environment；Binder materials sulphur used is petroleum by-product, and material can complete cycling and reutilization.
Description
Technical field
The invention belongs to building material field, more particularly, to a kind of modified sulfur in lifting sulphur concrete and sulphur
Application in sulphur mortar compression strength, anticorrosive and/or anti-permeability performance.
Background technology
Sulphur concrete, be it is a kind of use sulphur as binder materials, after admixing filler, aggregate by melting sulphur, with
Sulphur solidification, mixture cooling, the quick thermoplasticity construction material for obtaining intensity.Due to sulphur concrete have it is high-strength, low
The characteristic such as infiltration, antiacid alkali, endurance, quick setting, is widely used in the bases such as civilian, industrial and communications and transportation in the world
In Facilities Construction.
The corrosion resistance and anti-permeability performance of normal silicate concrete are often poor, such as acid corrosion-resistant performance extreme difference.
And in city and industrial production area, sour environment generally existing.It is reported that acid corrosion sewage conduct is tieed up every year in the U.S.
The expense repaiied reaches 25,000,000,000 dollars, or even the estimated cost than building new sewage conduct every year is taller.As the mankind are adapted from
So activity is increasingly frequent, and the acceleration of modernization, environment is contaminated more and more, and corrosive atmosphere distribution is also more next
It is more extensive.And the anticorrosive and anti-permeability performance of sulphur concrete is splendid, there is good durability.
Sulphur concrete also possesses the performance that many silicate concretes do not possess, and can make up it and apply in many aspects
Deficiency, while have silicate concrete other many good characteristics concurrently again, this cause sulphur concrete become it is a kind of very
Potential high performance building materials.Meanwhile the green building material that sulphur concrete is prepared as a kind of petroleum by-product, having can
The characteristic recycled, and the production of portland cement can produce a large amount of CO2So that sulphur concrete, which more conforms to future, to be held
The scientific idea of supervention exhibition.Therefore sulphur concrete can turn into a kind of good substitute of silicate concrete.
The content of the invention
It is an object of the present invention to provide a kind of modified sulfur lifting sulphur concrete and sulphur-bonded mortar compression strength,
Application in anticorrosive and/or anti-permeability performance.Using modified sulfur as partial gelation material, apply it and preparing modification
In sulphur concrete and modified sulfur mortar, both compression strength and antiacid caustic corrosion etc. are lifted.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of modified sulfur is in lifting sulphur concrete or sulphur-bonded mortar compression strength, anticorrosive and/or anti-permeability performance
Using, the modified sulfur is formed by the dicyclic pentylene modified sulphur of modifying agent, modifying agent account for the mass percent of sulphur for 1% ~
5%；Wherein, modified sulfur concrete includes following raw material by mass percentage：Modified sulfur 15%~20%, filler 12%~
27%, building stones 50%~60%, sand 18%~28%；Modified sulfur mortar includes following raw material according to the mass fraction：Modified sulfur 20%
~37%, filler 15%~48%, sand 50%~75%.
Preferably, the mass percent that modifying agent accounts for sulphur is 3%, and modified sulfur concrete includes by mass percentage
Following raw material：Modified sulfur 15%, filler 13.5%, building stones 51%, sand 20.5%.
Preferably, modifying agent account for sulphur mass percent be 3%, modified sulfur mortar by mass percentage include with
Lower raw material：Modified sulfur 24%, filler 21.6%, sand 54.4%.
Preferably, the filler is one or more in silica flour, flyash, miberal powder, cement micro-powder, packing specific area
Not less than 300 m2/kg。
Preferably, the sand is the one or more in river sand, quartz sand, Machine-made Sand.
The modified sulfur concrete is prepared by following steps：
S1. sulphur is heated under melting temperature, adds modifying agent and reacted, obtain modified sulfur；
S2. under melting temperature, modified sulphur is well mixed with the filler being accordingly preheated；
S3. under melting temperature, add the building stones preheated in advance in the compound obtained to S2 and sand stir after poured
Build operation；
Wherein, melting temperature is 130 DEG C~150 DEG C in step S1~S3, and the reaction time is 1~3h in step S1；
Preferably, melting temperature is 140 DEG C in step S1~S3, and the reaction time is 2h in step S1.
The modified sulfur mortar is prepared by following steps：
S1. sulphur is heated under melting temperature, adds modifying agent and reacted, obtain modified sulfur；
S2. under melting temperature, modified sulphur is well mixed with the filler being accordingly preheated；
S3. added under melting temperature, in the compound obtained to S2 after the sand preheated in advance stirs and carry out pouring work
Industry；
Wherein, melting temperature is 130 DEG C~150 DEG C in step S1~S3, and the reaction time is 1~3h in step S4.
Preferably, melting temperature is 140 DEG C in step S1~S3, and the reaction time is 2h in step S4.
Compared with prior art, the advantage of the invention is that：
1. modified sulfur concrete of the present invention is in terms of mechanical property, including compression strength, rupture strength, fatigue life
Deng normal silicate concrete is all substantially better than, compression strength is more than 80MPa；High-strength modified sulfur mortar compression strength exceedes
60MPa；
2. modified sulfur concrete of the present invention and modified sulfur mortar with respect to silicate concrete, have splendid antiacid
Corrosive nature and permeability resistance, performance all almost is resisted with splendid to all acid, salting liquid environment；
3. modified sulfur concrete of the present invention and modified sulfur mortar need not conserve, rate of set is exceedingly fast, Ji Ge little
When can reach the 80% of final strength, can reaches more than the 90% of final strength within one day；
4. modified sulfur concrete of the present invention and modified sulfur mortar can carry out pouring operation under refrigerated environment；
5. modified sulfur concrete of the present invention and modified sulfur mortar do not need water when preparing, in water shortage arid area
It is the splendid substitute of silicate concrete；
6. modified sulfur concrete of the present invention and modified sulfur mortar are green, glue is used as using petroleum by-product
Solidifying material, can complete cycling and reutilization after material is integrally fused.
Modified sulfur concrete and modified sulfur mortar of the present invention are while possessing above-mentioned advantage, with silicon
Hydrochlorate concrete plasticity is strong, good integrity, convenient material drawing, it is cheap, be easy to the advantages such as construction, can be applied to build top
In structure and foundation structure, the higher corrosion resistant of the needs such as municipal sewage treatment facility, industrial ground, maritime concrete is also applied for
Lose, in the environment of impermeabilisation, possess society and economic benefits well.
Embodiment
The present invention is described in further detail with reference to embodiments, but the implementation of the present invention is not limited to this.
Embodiment 1
The preparation of high-strength modified sulfur concrete, by mass percentage, sulphur are the 15% of gross mass, wherein modifying agent DCPD
The 3% of sulphur quality is accounted for, cement accounts for the 13.5% of gross mass, and river sand accounts for the 20.5% of gross mass, and granite coarse aggregate accounts for gross mass
51%。
Step 1：At 140 DEG C, by sulfur melting, the DCPD for weighing its quality 3% afterwards is added thereto reaction 2h.
Step 2：It is at 140 DEG C, the modified sulphur that step 1 obtains and accordingly warmed-up cement filler is uniform
With conjunction.
Step 3：At 140 DEG C, the river sand preheated in advance and granite stirring are added in the compound obtained to step 2
Uniformly, 60 seconds after-pourings are vibrated into warmed-up cast iron die trial, the form removal after normal temperature cools down 1d.
Such a modified sulfur concrete sample 3d compression strength reaches 82.5MPa, and mixture has preferable mobility.
Embodiment 2
The preparation of high-strength modified sulfur mortar, by mass percentage, sulfur content are the 24% of gross mass, wherein modifying agent
DCPD accounts for the 3% of sulphur quality, and cement accounts for the 21.6% of gross mass, and river sand accounts for the 54.4% of gross mass.
Step 1：At 140 DEG C, by sulfur melting, the DCPD for weighing its quality 3% afterwards is added thereto reaction 2h.
Step 2：It is at 140 DEG C, the modified sulphur that step 1 obtains and accordingly warmed-up cement filler is uniform
With conjunction.
Step 3：The river sand preheated in advance is added at 140 DEG C, in the compound obtained to step 2 to stir, and is shaken
60 seconds after-pourings are smash into warmed-up cast iron die trial, the form removal after normal temperature cools down 1d.
Such a modified sulfur mortar specimen 3d compression strength reaches 62.3MPa, and rupture strength reaches 11.9MPa.
Embodiment 3
This experiment is the research of modified sulfur concrete and modified sulfur mortar permeance property.Using ASTM C1202 code tests
Method is that electric flux method comes overall merit normal concrete and modified sulfur concrete, the chloride-penetration resistance of modified sulfur mortar
Property, the test specimen size of this method is Φ 100mm × 50mm, wherein, conserved under silicate concrete standard conditions to 28d ages,
Modified sulfur concrete takes out after conserving 1d at room temperature, is put under the full water installations of vacuum and first vacuumizes 3h, adds water and take out 1h, it
After continue soak 18h.The negative electrode and anode of test specimen are respectively provided with the NaCl solution that concentration is 3% and 0.3mol/L NaOH
Solution, then apply 60V DC voltage, the interior electricity Q values by test specimen of record 6h, to weigh in the axial direction of concrete sample
Measure the compaction rate of concrete and the ability of resistance chloride permeability.According to ASTM C1202 standard methods, modified sulphur is determined
Sulphur mortar and the electric flux of modified sulfur concrete room temperature maintenance 1d, 3d, 7d, 28d age, afterwards and silicate concrete（C50
And C100）The electric flux value of standard curing 28d ages is contrasted, to assess the Anti-Chloride Ion Penetration of each group test specimen.Electricity
Flux Q values are lower, show that the Anti-Chloride Ion Penetration of test specimen is better.
Experimental result is shown in Table 1, table 2.
The modified sulfur mortar of table 1（SPM）With modified sulfur concrete（SPC）Electric flux measured value
Note：G1 in form refers to the 5mm-10mm of Huizhou Shi Chang productions Guamishi；G2 refers to the 10mm-18mm of Huizhou Shi Chang productions flower
Hilllock rock rubble.
The electric flux measured value of the C50 and C100 silicate concretes of table 2
It was found from from Tables 1 and 2, modified sulfur mortar, the Anti-Chloride Ion Penetration of modified sulfur concrete are far better than silicon
Hydrochlorate concrete.Under this experiment condition, the 6h electric fluxes measured value of modified sulfur mortar is C50 silicate concretes
0.011 times, for 0.315 times of C100 silicate concretes；The 6h electric fluxes measured value of modified sulfur concrete is C50 silicon
0.018 times of hydrochlorate concrete, for 0.507 times of C100 silicate concretes.This is due to modified sulfur mortar and modification
Sulphur concrete has less hole, while modified sulfur matrix has extremely strong hydrophobicity, makes after wrapping particles of aggregates
Material be integrally difficult to it is permeable.By above experimental result, C50 silicate concrete impermeabilisation abilities are poor,
C100 silicate concretes then have preferable anti-permeability performance；And modified sulfur concrete and modified sulfur mortar is impervious
Permeability can then be much better than strength silicate concrete and C100 superelevation strength silicate concrete in C50.
Embodiment 4
This experiment is the research of modified sulfur concrete and modified sulfur mortar acid-alkali-corrosive-resisting performance.Use sulfuric acid, hydrochloric acid, phosphorus
The acid-base solutions such as acid, sodium hydroxide, test modified sulfur concrete, modified sulfur mortar, silicate concrete test specimen are in each height
The mass loss and loss of strength after 7d are soaked under the acid-base solution of concentration respectively, to characterize their antiacid caustic corrosion performance.
To study the difference that different corrosive deposits influence on test specimen, this experiment is using the different etchant molar concentrations of control
Mode is realized.It is 8mol/L sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide solution conduct immersion etchant to use molar fraction.
All test specimens use the cubic block of 7cm × 7cm × 7cm sizes.A 1000mL beaker is used alone as appearance in each test specimen
Device, beaker are preserved using preservative film covering rim of a cup, to prevent etchant from volatilizing and absorb moisture.
The used sulfuric acid of experiment, hydrochloric acid, phosphoric acid, sodium hydroxide are AR：
The mass fraction for analyzing the pure concentrated sulfuric acid is 98%, density 1.84g/mL, H2SO4Molecular weight be 98, molar concentration used
For：1.84×1000×0.98/98=18.4mol/L.
Between the mass fraction for analyzing pure hydrochloric acid is 36% to 38%, density 1.19g/mL, HCl molecular weight are 36.5,
Molar concentration used is：1000×0.37×1.19/36.5 =12.063mol/L.
Pure phosphoric acid solution is analyzed, phosphorus acid content >=85%, when calculating concentration in terms of 85%, the density of phosphoric acid is 1.69, point
Son amount is 98, and molar concentration used in analysis pure phosphoric acid solution is：1000×1.69×85%/98=14.7mol/L.
Sodium hydroxide solution is prepared using AR, and NaOH content is more than 98%.
The 8mol/L etchants of corresponding soda acid are prepared according to above-mentioned molar concentration.After the good each etchant of configuration, first each
500mL etchants are poured into 1000mL beakers, place into corresponding test specimen, are sealed in preservative film in 20 DEG C of environment, etchant
Solution concentration is no longer adjusted after preparation.Modified sulfur concrete, modified sulfur mortar conserve 3d at room temperature, and silicate coagulation
Native test specimen then starts after standard curing 7d to soak erosion test.Specific modified sulfur concrete（SPC）, modified sulfur mortar
（SPM）, C50 silicate concretes（PCC）Proportioning is shown in Table 3：
Table 3 SPC, SPM, PCC are matched
Note：G1 in form refers to the 5mm-10mm of Huizhou Shi Chang productions Guamishi；G2 refers to the 10mm-18mm of Huizhou Shi Chang productions flower
Hilllock rock rubble.
Experimental result is shown in Table 4 and table 5.
Mass losses of table 4 SPC, SPM, the PCC after different solutions soak 7d
Losss of strength of table 5 SPC, SPM, the PCC after different solutions soak 7d
To modified sulfur concrete, modified sulfur mortar, silicate concrete respectively in sulfuric acid, phosphoric acid, hydrochloric acid, hydrogen more than
The mass loss after 7d is soaked in sodium hydroxide solution, the result of loss of strength is understood：
（1）Under this experiment condition, in 8mol/L sulfuric acid, hydrochloric acid, phosphoric acid erosion environment, modified sulfur concrete and modification
The quality of sulphur-bonded mortar is barely affected, and loss of strength is smaller, and only up to 3.9%；Corroded in 8mol/L sodium hydroxide
Under, the quality of modified sulfur concrete and modified sulfur mortar has certain loss, but mass loss amount is smaller in a short time, intensity
Loss is also smaller, and up to 6.7%.
（2）Under this experimental condition, in the sulfuric acid, hydrochloric acid erosion environment in 8mol/L, the corrosion of silicate concrete compared with
To be serious, mechanical properties decrease is very big, and up to 56.4%；In the case where phosphoric acid corrodes in short term, performance degradation is smaller；In 8mol/L hydrogen-oxygen
Change under sodium solution corrodes in short term, its quality and apparent almost unchanged, but mechanical property has larger decline, have dropped 24.5%.
（3）Under this experimental condition, hydrochloric acid is invaded modified sulfur concrete, modified sulfur mortar, silicate concrete
Erosion degradation effects are all better than the sulfuric acid and phosphoric acid solution of same concentrations, and this is probably that villaumite is big by concrete or mortar leaching speed
Caused by sulfate, phosphate.
（4）Modified sulfur concrete, the acid resistance performance of modified sulfur mortar are just short far better than silicate concrete
Its alkali resistant erosion performance is also better than silicate concrete for phase intensity.
Comparative example 1
Two kinds of modifying agent of DCPD and Styrene in embodiment are used respectively, are studied when they singly mix to sulphur-bonded mortar
Modified effect.All glue sand test specimens substitute sulphur quality respectively using 70% river sand and the proportioning of 30% sulphur, control DCPD
1%, 3%, 5%, Styrene substitute 1%, 5%, the 10% of sulphur quality respectively.Experiment is used uniformly 4cm × 4cm × 16cm's
Standard specimen, preparing test specimen, maintenance carries out rupture strength and compression strength examination to 1d, 3d, 7d, 28d respectively at room temperature afterwards
Test.Sulphur-bonded mortar prepares code with reference to American Society Testing and Materials's ASTM C287-98 standards.
DCPD and Styrene volumes the results are shown in Table 6, table 7 to the performance impact of sulphur-bonded mortar.
Performance impact of the DCPD volumes of table 6 to sulphur-bonded mortar
Performance impact of the Styrene volumes of table 7 to sulphur-bonded mortar
It was found from from table 6 and table 7, the resistance to compression of pure sulphur-bonded mortar and rupture strength change with age it is on a declining curve, 28d resistance to compressions and
Rupture strength is respectively 20.1MPa and 4.1MPa, and 28d compares 1d and have dropped 20.9% and 28.7% respectively.DCPD volumes are 3%
When, sulphur-bonded mortar 28d compression strength and rupture strength are maximum, respectively 51.7MPa and 11.9MPa, compared to pure sulphur-bonded mortar point
157.2% and 190.2% are not improved.The resistance to compression and rupture strength for mixing DCPD sulphur-bonded mortar change over time less, 1d
When with respect to bright sulfur sulphur group compression strength maximum lift amplitude just up to 98.4%.The resistance to compression of DCPD sulphur-bonded mortars and rupture strength 1d
It can reach more than the 80% of 28d.The compression strength for mixing Styrene sulphur-bonded mortar is bright as age growth has in 1d~7d
Then there is the situation of overall stability in aobvious growth trend, 7d~28d.When Styrene volumes are more than 1%, the early stage of sulphur-bonded mortar
Compression strength weakens with the increase of incorporation, and when Styrene incorporations are 1%, the compression strength of sulphur-bonded mortar is in any age
Best compressive property is all shown, bright sulfur sulphur group is compared in 28d ages and improves 75%.And the volume groups pair of Styrene 10%
The rupture strength lifting of sulphur-bonded mortar is best, and 28d compares bright sulfur sulphur group and improves 148.7%.Contrast DCPD and Styrene
Two kinds of sulfur modifiers are can be found that：During 28d, preferably lifting effects of the DCPD for sulphur-bonded mortar compression strength and rupture strength
Fruit is 2 times and 1.3 times that Styrene preferably lifts effect respectively.DCPD is for sulphur-bonded mortar either resistance to compression or anti-folding
Performance has the lifting effect more stable and higher than Styrene.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of modified sulfur is in lifting sulphur concrete or sulphur-bonded mortar compression strength, anticorrosive and/or anti-permeability performance
Application, it is characterised in that modified sulfur is formed by the dicyclic pentylene modified sulphur of modifying agent, and modifying agent accounts for the quality hundred of sulphur
Divide than being 1% ~ 5%；Wherein, modified sulfur concrete includes following raw material by mass percentage：Modified sulfur 15%~20%, is filled out
Material 12%~27%, building stones 50%~60%, sand 18%~28%；Modified sulfur mortar includes following raw material according to the mass fraction：It is modified
Sulphur 20%~37%, filler 15%~48%, sand 50%~75%.
2. modified sulfur according to claim 1 lifting sulphur concrete or sulphur-bonded mortar compression strength, it is anticorrosive and/
Or the application in anti-permeability performance, it is characterised in that the mass percent that modifying agent accounts for sulphur is 3%, and modified sulfur concrete is pressed
Mass percentage includes following raw material：Modified sulfur 15%, filler 13.5%, building stones 51%, sand 20.5%.
3. modified sulfur according to claim 1 lifting sulphur concrete or sulphur-bonded mortar compression strength, it is anticorrosive and/
Or the application in anti-permeability performance, it is characterised in that the mass percent that modifying agent accounts for sulphur is 3%, and modified sulfur mortar presses matter
Amount percentage meter includes following raw material：Modified sulfur 24%, filler 21.6%, sand 54.4%.
4. lifting sulphur concrete or sulphur-bonded mortar compression strength according to any described modified sulfur of claims 1 to 3, resisting
Application in corrosion and/or anti-permeability performance, it is characterised in that the filler is silica flour, flyash, miberal powder, cement micro-powder
Middle one or more, and the specific surface area of filler is not less than 300 m2/kg。
5. lifting sulphur concrete or sulphur-bonded mortar compression strength according to any described modified sulfur of claims 1 to 3, resisting
Application in corrosion and/or anti-permeability performance, it is characterised in that the sand is river sand, quartz sand, one kind in Machine-made Sand or more
Kind.
6. modified sulfur according to claim 1 or 2 is in lifting sulphur concrete or sulphur-bonded mortar compression strength, anticorrosive
And/or the application in anti-permeability performance, it is characterised in that modified sulfur concrete is prepared by following steps：
S1. sulphur is heated under melting temperature, adds modifying agent and reacted, obtain modified sulfur；
S2. under melting temperature, modified sulphur is well mixed with the filler being accordingly preheated；
S3. under melting temperature, add the building stones preheated in advance in the compound obtained to S2 and sand stir after poured
Build operation；
Wherein, melting temperature is 130 DEG C~150 DEG C in step S1~S3, and the reaction time is 1~3h in step S1.
7. modified sulfur according to claim 6 lifting sulphur concrete or sulphur-bonded mortar compression strength, it is anticorrosive and/
Or the application in anti-permeability performance, it is characterised in that melting temperature is 140 DEG C in step S1~S3, the reaction time in step S1
For 2h.
8. modified sulfur according to claim 1 or 3 is in lifting sulphur concrete or sulphur-bonded mortar compression strength, anticorrosive
And/or the application in anti-permeability performance, it is characterised in that modified sulfur mortar is prepared by following steps：
S1. sulphur is heated under melting temperature, adds modifying agent and reacted, obtain modified sulfur；
S2. under melting temperature, modified sulphur is well mixed with the filler being accordingly preheated；
S3. added under melting temperature, in the compound obtained to S2 after the sand preheated in advance stirs and carry out pouring work
Industry；
Wherein, melting temperature is 130 DEG C~150 DEG C in step S1~S3, and the reaction time is 1~3h in step S3.
9. modified sulfur according to claim 8 lifting sulphur concrete or sulphur-bonded mortar compression strength, it is anticorrosive and/
Or the application in anti-permeability performance, it is characterised in that melting temperature is 140 DEG C in step S1~S3, the reaction time in step S4
For 2h.
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| 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 |
| CN113199593A (en) * | 2021-05-19 | 2021-08-03 | 暨南大学 | Process for preparing high-strength modified sulfur concrete by cold water bath vibration forming method |
| US11932578B1 (en) * | 2022-11-08 | 2024-03-19 | Wuhan University Of Technology | Granite stone powder phosphoric acid-based geopolymer and preparation method thereof |
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| US11932578B1 (en) * | 2022-11-08 | 2024-03-19 | Wuhan University Of Technology | Granite stone powder phosphoric acid-based geopolymer and preparation method thereof |
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| CN107540336B (en) | 2020-05-08 |
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