CN106565124A - Expanded alkyl air entraining agent - Google Patents
Expanded alkyl air entraining agent Download PDFInfo
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Abstract
The invention discloses an expanded alkyl air entraining agent. The expanded alkyl air entraining agent consists of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, calcium bentonite and flyash. The expanded alkyl air entraining agent has the advantages that the air entraining agent has the characteristics of good stability, good dispersibility, excellent air entraining performance and good quality of air bubbles, after the expanded alkyl air entraining agent is used in concrete, long-term performance and durability such as freezing and thawing resistance, permeability resistance and carbonation resistance of concrete can be greatly improved, and the expanded alkyl air entraining agent has good technical economic benefits.
Description
Technical field
The present invention relates to a kind of air entraining agent, specifically a kind of swollen alkyl air entraining agent, belong to air entraining agent field.
Background technology
A kind of additive of the air entraining agent as concrete, can not only improve workability of concrete, and can increase substantially the frost-proof test of xoncrete structure, be that the concrete works in freezing-thawing solves most basic most distinct issues.Foreign countries are beginning to the research and development to air entraining agent very early, domestic air entraining agent development and Application is started late, but also there is rosin to include colophonium pyrolytic polymer at present, rosin soap air-entraining agent, code name is 801, the anion surfactant of 901-A, the air entraining agent of the types such as SJ Fructus Gleditsia classes, and achieve in each large-engineering and be widely applied very much, but existing air entraining agent mostly is the technology and product of Introduced From Abroad air entraining agent, the air entraining agent of good performance of domestic independent development is few in number, the needs of China's modernization construction are not adapted to, therefore develop best in quality, stable performance, the superior new varieties air entraining agent of technology and economic effect has been concrete works problem demanding prompt solution.
The content of the invention
In order to solve the above problems, the present invention devises a kind of swollen alkyl air entraining agent, the characteristics of good stability, good dispersion, bleed function admirable, good bubble quality, after being applied in concrete, long-term behaviour and the endurance qualities such as the freezing and thawing performance of concrete, permeability resistance, anti-carbonation properties can be greatly improved, with good Technical Economy benefit.
The technical scheme is that：
Swollen alkyl air entraining agent, is made up of the raw material of following weight portion：
Foaming agent 1：Alkyl surfactants 1 are dodecylbenzene sodium sulfonate, and consumption is 2 parts；
Foaming agent 2：Alkyl surfactants 2 are sodium lauryl sulphate, and consumption is 3 parts；
Stabilizer：Containing Ca2 +The inorganic material of ion is calcium-base bentonite, and consumption is 3 parts；
Dispersant：Fine-ground fly-ash, consumption are 2 parts.
Concrete ratio is dodecylbenzene sodium sulfonate：Sodium lauryl sulphate：Calcium-base bentonite：Flyash=2:3:3:2.
Wherein, the specific surface area of the flyash is 485.
The swollen alkyl air entraining agent of the present invention is using surfactant and stabilizer under normal temperature state, according to the surfactant ratio 1 different with stabilizer：1, mixing is stirred in additive complex device, makes two kinds of solution occur to interact, the compounding air entraining agent type required for completing.Verified with the organic material containing alkyl surfactants repeatedly through lot of experiments and contain Ca2 +The inorganic material of ion is compound to be made.The air entraining agent belongs to ion-type, they with certain electrically, so bubble is after the marshalling of liquid film both sides, like charges are mutually exclusive, make bubble be difficult further towards；Ca in air entraining agent2 +Ion forms calcium precipitation in cement mortar solution, when this sludge concentration around the fine cement granules and on bubble chamber film is appropriate, the thicknesses of layers and mechanical strength of the liquid film formed around bubble can be increased, this just makes the merging of bubble become difficult, prevents bubble-break.
It is an advantage of the current invention that：Through numerous studies test, analytic demonstration and practical application, by preferred foaming agent, stabilizer and dispersant and the corresponding synthesis technique of design, have developed novel high-performance air entraining agent --- swollen alkyl air entraining agent, relative to commercially available common air entraining agent, the characteristics of with good stability, good dispersion, bleed function admirable, good bubble quality, after being applied in concrete, long-term behaviour and the endurance qualities such as the freezing and thawing performance of concrete, permeability resistance, anti-carbonation properties can be greatly improved, with good Technical Economy benefit.
With reference to specific embodiment, the invention will be further described.
Specific embodiment
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.
Unless otherwise stated, the percent employed in the present invention is percetage by weight.
Embodiment 1
Swollen alkyl air entraining agent
According to alkyl surfactants and contain Ca2 +Stabilizer different proportion, carry out foam height, bubble bubble diameter, form, foam time test determine the optimum composition of air entraining agent；
Consider according in concrete 4% air content（According to lot of experiments and proof is expounded through peer review, when Air Content of Air-entrained Concrete reaches 4% or so, the endurance quality such as anti-freezing property of concrete reaches most preferably）, the test of concrete mixture characteristic, mechanical performance of concrete and endurance performance of concrete is carried out, the optimum mix amount of the air entraining agent is determined.
First, concrete charge pass test
By determining the electricity by concrete sample, the ability of agent on crack resistance of concrete chloride permeability is evaluated；The instrument and equipment for adopting is RCM-F multifunctional concrete permeability comprehensive test apparatus；
Test procedure：By the cylinder concrete sample of 100 × 50mm of Φ, after mark is supported, taking-up is put into vacuum tank evacuation 3 hours, after the full water immersion of injection distilled water, in test specimen one end immersion 0.3mol/LNaOH solution（Positive pole）, in other end immersion 3%NaCl solution（Negative pole）, and apply and keep 60V DC voltages at two ends, test the total electricity for passing through for 6 hours（In units of coulomb）
Table 1 is according to the electricity qualitative evaluation concrete resistance permeating of Cl rank for passing through
| The electricity for passing through（Coulomb） | Chloride permeability |
| More than 4000 | It is high |
| 2000---4000 | It is medium |
| 1000---2000 | It is low |
| 100---1000 | It is very low |
| Less than 100 | It is negligible |
2nd, air entraining agent foam performance test
1st, foam fineness：Air entraining agent is dissolved in the water with finite concentration, is started foam blender, after stirring certain hour, is observed foam fineness and foaming quality；
As a result：By swollen alkyl air entraining agent（M）With commercially available Fructus Gleditsia glycoside air entraining agent（P）Respectively compare 1 with foam water：50（That is the mass ratio of air entraining agent and water）It is soluble in water, 5min is stirred with certain speed in foam blender respectively, observation produces the quality of the fineness of foam and foaming.The result of range estimation shows, the foam that M and P is produced is all very abundant, but the bubble that M is produced is more uniform, fine and closely woven, and the bubble that P is produced size of comparing is uneven, it is quiet stop 30min after, the bubble abatement of P is also fast than M.From macroscopically illustrating under the same terms, the bubble bubble diameter that M is introduced is little for this, and toughness preferably, is not easily broken.
It is explained above M better than the bubble stability of P, traces it to its cause：
It is because that M belongs to ion-type air entraining agent, they are electrical with certain.So air entraining agent is after the both sides marshalling of liquid film, their like charges are mutually exclusive, make to be difficult between bubble further towards.Contain Ca in M2+The inorganic material of ion component, Ca2+Ion forms calcium precipitation in cement mortar solution, when this sludge concentration around the fine cement granules and on bubble chamber film is appropriate, the thicknesses of layers and mechanical strength of the liquid film formed around bubble can be increased, this just makes the merging of bubble become difficult, prevents bubble-break.
2nd, coefficient of foaming：The foam produced by foam blender is filled in the bottomless glass tank of a constant volume, two ends strike off, claim its weight.Coefficient of foaming M can be calculated as follows：
M=Vγ/（G2–G1）
In formula：M refers to coefficient of foaming；V refers to glass tank volume（cm3）；γ refers to bubble solution density（It is similar to 1g/cm3）；G1 refers to glass tank quality（g）；G2 refers to glass tank and foam quality（g）；
As a result see the table below：
2 coefficient of foaming of table
| Air entraining agent type | Coefficient of foaming |
| P | 125 |
| M | 167 |
Result above is indicated under the same terms, and the foaming capacity of M is more than P, and when used in concrete, M is obtained with suitable amount of air entrainment with less volume.
3rd, foam height：Using international and domestic general Ross method（Ross-Milles methods）To detect the foamability of air entraining agent.Its test procedure is：Supplied water using water bath with thermostatic control, the temperature stabilization of Roche foam meter pipe box water-bath is made at 40 ± 0.5 DEG C；Roche foam meter scale inside pipe wall is cleaned with distilled water, is rinsed and then tube wall must be rinsed with test solution completely, it is also necessary to rinses complete；Graded tube piston is closed, with other minim pipette injection 50ml test solutions to 50ml scales（This test solution must also be previously heated to 40 DEG C）；Minim pipette is filled into 200ml test solutions, this test solution is previously heated to 40 DEG C；Minim pipette being arranged on prior ready pipe support with the section of graded tube into vertical configuration, solution stream being made to the center of graded tube, the outlet of minim pipette should be placed on 900mm graduation marks；The piston of minim pipette is opened, flows down solution.When the solution stream in minim pipette is complete, foam height is determined immediately；
The foam stabilizing time（Partly disappear the time）：In the test of Ross method, with foam height cut down to liquid stream stop when foam height half when time representing；
As a result see the table below：
Table 3 is using the foam height of Ross method detection, sedimentation away from, bleeding quantity, foam stabilizing time
| Air entraining agent type | Foam height mm | 30min foams decline mm | 60min foams decline mm | 30min bleeding height mm | 60min bleeding height mm | Foam stabilizing time min |
| P | 700 | 150 | 540 | 0 | 174 | 40 |
| M | 730 | 0 | 0 | 0 | 90 | 110 |
As the country is with regard to the examination criteria and method confusion of foaming capacity, in order to characterize the foamability and bubble holding capacity of air entraining agent comprehensively, the detection for again foam height of two kinds, sedimentation being carried out away from, bleeding quantity, foam stabilizing time using Ross method, table NO results show, the foam height of M is more than P, and the foaming capacity for also demonstrating M is preferable；Prove As time goes on from drop data under the foam height of 30min, 60min, the bubble of P is easier rupture, and the bubble of M then pliability preferably, is not easily broken；The bleeding of 30min, 60min highly also show the fragile fragility that P produces bubble relative to M.Foam stabilizing time P is 40min, and M is 110min, is indicated after mixing in concrete, and the bubble that M is introduced has more preferable stability, is not easy to vanish or escapes in concrete-agitating with process of vibrating.
3rd, air entraining agent mixes service check after concrete
Using the same C40 concrete mixs of actual production, performance test is carried out to the concrete of normal concrete, air-entrained agent P, air-entrained agent M.Concrete mix is as follows：
4 actual production concrete mix of table
| Numbering | CB | C | KM | W | S | G | FDN | MG | Air entraining agent type | Air entraining agent volume % | BS | ρ |
| A | 410 | 328 | 82 | 170 | 729 | 1141 | 1.0 | 0.1 | / | / | 0.39 | 2450 |
| B | P | 0.6 | ||||||||||
| C | M | 0.03 |
Note：P.O42.5R cement；One-level is matched somebody with somebody；KM-fine-ground fly-ash；FDN-naphthalene series high-efficiency water-reducing agent；MG-calcium lignosulfonate；BS-sand coarse aggregate ratio；Additive is added in the ratio of Binder Materials；
1st, concrete mix workability, bleeding rate and slump-loss
Concrete mixture characteristic result of the test is shown in Table 5：
Impact of 5 air entraining agent of table to concrete mixture characteristic
Result concrete mixture characteristic affected from upper table air entraining agent：After air entraining agent is mixed in concrete, the workability of concrete improves, mobility increase.This is that a large amount of small and independent bubbles can be introduced in concrete due to air entraining agent, these spherical bubbles are as ball, change scraping mechanism when performing relative motion between inside concrete gathers materials, become the sliding friction between gathering materials into rolling friction, internal friction resistance is reduced, this just makes fresh concrete have more preferable workability and mobility.Further, since bubble adsorbs on cement particle surface, increase the surface area of cement particle, cause system viscosity to increase, floating support and supporting role of the bubble to fine aggregates in addition mitigates all can concrete water bleeding and sedimentation phenomenon.
But, different type air entraining agent is also different for the effect of concrete mix, as can be seen from the results of table 5, air entraining agent M is compared to P so that concrete mix slump-loss, divergence, air content loss have more preferable performance, and the foam performance result of the test of this and air entraining agent made above is one-to-one.Such as test number B, after air entraining agent P adds concrete, when concrete mix goes out machine, the slump, divergence and air content are still all satisfactory, but elapse over time, due to bubble effusion and rupture in a large number, after 1h, concrete mix air content is rapidly decreased to 2.5%, and mixture is also lost flowability gradually, and such performance is the actual requirement that can not meet production at all.After concrete mix goes out machine, through transport to building site, again through vibrating after pouring, air content can be in haulage time, pumping pressure, lose when the effect of vibrating, this pliability that bubble in concrete mix is introduced into air entraining agent proposes very high request, obviously, air entraining agent P can not meet requirement, good behaviour when going out machine is a kind of illusion, real introduced in xoncrete structure number of bubbles after concreting is extremely limited, not having this plays the role of, and M then volume is little, bleed performance and holding capacity are excellent, it is a kind of high performance air entraining agent.
2nd, impact of the air entraining agent to compressive strength of concrete
6 compressive strength of concrete of table
| Numbering | 28d cubic compressive strength MPa |
| A | 60.4 |
| B | 54.9 |
| C | 56.8 |
Result compressive strength of concrete affected from upper table air entraining agent：After air entraining agent is mixed in concrete, 28d cubic compressive strengths have and to a certain degree decline, and B have dropped 9.1%, C and have dropped 6.0%, show that M is slightly better than P.
4th, agent on crack resistance of concrete freeze thawing performance test
According to specification GBJ82-85《Standard for test methods of longterm performance and durability of ordinary concrete》Carry out concrete fast freeze-thaw test, sample dimensions：100mm×100mm×400mm.
Molding freeze thawing resistance test specimen is distinguished to test number A, B, C, concrete fast freeze-thaw test after 28d curing ages, is carried out, result of the test is as shown in table NO：
7 agent on crack resistance of concrete freeze thawing result of the test of table
| Numbering | Freeze thawing resistance number of times | Freeze-thaw damage state |
| A | 50 | Brittle failure |
| B | 150 | Surface slurry is peeled off |
| C | 350 | Surface slurry is peeled off |
From 7 agent on crack resistance of concrete freeze thawing result of the test of table：The normal concrete freezing and thawing performance for being not spiked with air entraining agent is poor, freeze thawing resistance number of times only has 50 times, and when destroying, there is brittle failure phenomenon, this is because when concrete is endured cold, under the effect of ice swelling pressure, the pressurized tailing edge capillary channel of moisture is internally migrated, and just generates hydrostatic pressure when migrating constrained, inside concrete vulnerable area is made to produce microcrack, constantly extension just there occurs brittle failure phenomenon to microcrack.After adding air entraining agent, the a large amount of bubbles for introducing alleviate ice swelling pressure and osmotic pressure, prevent freeze-thaw damage, therefore the freezing and thawing performance of concrete is improved, but in surface portion, because there is volumetric expansion and cause surface layer of slurry to be peeled off in first contact wetting, the water freezing in some surface voids.From 7 result of table this it appears that P and M is for the difference of agent on crack resistance of concrete freeze thawing performance.
5th, agent on crack resistance of concrete permeability can be tested
According to China's specification GBJ82-85《Standard for test methods of longterm performance and durability of ordinary concrete》Carry out concrete impermeability test, sample dimensions：Top surface Φ 175mm, bottom surface Φ 185mm, high 150mm.Test piece maintenance is taken out to the previous day is tested, and surface is dried, and then applies one layer of encapsulant in its side, and immediately on pressue device, during test specimen Specimen is covered, after a while, pressure relief is sleeved on Anti-leakage instrument together with test specimen and is tested.
Molding impermeabilisation test specimen is distinguished to test number A, B, C, concrete impervious permeability test after 28d curing ages, is carried out, result of the test is as shown in table 8：
8 agent on crack resistance of concrete permeability result of the test of table
| Numbering | Seepage-resistant grade | Average infiltration height mm |
| A | P8 | 50 |
| B | P10 | 38 |
| C | P10 | 14 |
From 8 agent on crack resistance of concrete permeability result of table：Due to the progress of modern concrete technology, admixture, high efficiency water reducing agent application it is very universal, therefore the permeability resistance of concrete is also strengthened, but a part is still suffered from concrete makes concrete mix obtain the free water of workability, these moisture can rest on inside concrete after concreting is vibrated, and be gathered in below coarse aggregate, after the concrete is cured the phase be evaporated and form internal voids or gap, therefore, the permeability or objective reality of concrete.After air entraining agent is mixed in concrete, not only mixture workability is improved, prevent bleeding and sedimentation isolation, make to gather materials and reduce with the big pore on cement stone interface, and a large amount of micro-bubbles that bleed is produced are distributed in the space in xoncrete structure, and come together on the road of capillary tube more, cut off capillary tube, therefore, the permeability resistance of concrete is significantly improved.From upper table concrete, after incorporation air entraining agent, the raising of concrete impervious grade and the reduction of average infiltration height can also draw two types air entraining agent for the difference of agent on crack resistance of concrete permeability energy.
6th, concrete charge pass test
In order to the enhancing more accurately to mixing agent on crack resistance of concrete permeability after air entraining agent is verified, we employ test method-concrete charge pass test method(s) more advanced now, by determining the electricity by concrete sample, the ability of agent on crack resistance of concrete chloride permeability is evaluated.Result of the test is shown in Table 9：
9 concrete charge pass result of the test of table
| Numbering | Electric flux C | Permeability values |
| A | 1239 | It is low |
| B | 974 | It is very low |
| C | 622 | It is very low |
The actual anti-permeability performance of concrete now can not be accurately evaluated in traditional impermeabilisation evaluation methodology, and electric flux test rule can more accurately evaluate the ability that concrete resists chloride permeability, visible by 9 result of the test of table：Normal concrete, admixture different type air entraining agent inside concrete degree of compaction it is different, therefore the resistance of concrete to chloride ion penetration is different, air entraining agent is had to the potentiation of agent on crack resistance of concrete permeability compared with science, the accurate, evaluation of value and is compared by electric flux test.
7th, agent on crack resistance of concrete carbonation properties test
Molding carbonization test test specimen is distinguished to test number A, B, C, it is stipulated that agent on crack resistance of concrete carbonation properties test is carried out after curing age, result of the test is as shown in table 10：
10 agent on crack resistance of concrete carbonization test result of table
From 10 agent on crack resistance of concrete carbonization test result of table：After air-entrained agent, the anti-carbonation properties of concrete make moderate progress, wherein C（Air-entrained agent M）Again compare B（Air-entrained agent P）It is slightly good.The reason for agent on crack resistance of concrete carbonation properties improve after air-entrained agent still can be improved with concrete density, permeability resistance be strengthened to explain.
8th, concrete air-void spacing factor
The air-void spacing factor of table 11 concrete B, C
| Numbering | Air-void spacing factor μm |
| B | 82.9 |
| C | 56.0 |
From the result of 11 data of table：Same concrete mix, raw material is also identical, after air entraining agent P and M mix concrete, the difference of micro structure bubble distribution in maturing, bubble diameter in concrete B, air-void spacing factor is big than C, and this sees the reason for demonstrating the difference of air entraining agent P and M bleed ability and thus bring agent on crack resistance of concrete freeze thawing performance difference in angle from thin.
9th, concrete electric scarnning mirror test
By Xinjiang Agricultural Univ Electronic Speculum to mix air entraining agent after, the internal microstructure of maturing, hydrated product distribution situation are observed.
Observe from microcosmic, the hydrated product of air-entrained agent M than air-entrained agent P with finer and close accumulation and arrangement.These further demonstrate the superperformance and the potentiation to agent on crack resistance of concrete permeability energy of P from the angle of microcosmic.
It is raw materials used in the present invention to be conventional raw material in the production of this area, can obtain from market, and for production result will not produce impact；
The operation of the various equipment employed in the present invention, the conventional equipment being used in the production technology of this area, and each equipment, parameter etc. are carried out according to routine operation, have no special feature.
Finally it should be noted that：The foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, which still can be modified to the technical scheme described in foregoing embodiments, or carry out equivalent to which part technical characteristic.All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included within the scope of the present invention.
Claims (2)
1. swollen alkyl air entraining agent, it is characterised in that be made up of the raw material of following weight portion：
Foaming agent 1：Alkyl surfactants 1 are dodecylbenzene sodium sulfonate, and consumption is 2 parts；
Foaming agent 2：Alkyl surfactants 2 are sodium lauryl sulphate, and consumption is 3 parts；
Stabilizer：Containing Ca2 +The inorganic material of ion is calcium-base bentonite, and consumption is 3 parts；
Dispersant：Fine-ground fly-ash, consumption are 2 parts.
2. swollen alkyl air entraining agent according to claim 1, it is characterised in that：The specific surface area of the flyash is 485.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107263672A (en) * | 2017-07-11 | 2017-10-20 | 威信广厦模块住宅工业有限公司 | A kind of preparation method of cracking resistance sound-proof lightweight wall |
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Application publication date: 20170419 |