CN102517587A - Ethyl cellulose type calcium nitrite corrosion inhibitor and preparation method thereof - Google Patents
Ethyl cellulose type calcium nitrite corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN102517587A CN102517587A CN2011103787725A CN201110378772A CN102517587A CN 102517587 A CN102517587 A CN 102517587A CN 2011103787725 A CN2011103787725 A CN 2011103787725A CN 201110378772 A CN201110378772 A CN 201110378772A CN 102517587 A CN102517587 A CN 102517587A
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Abstract
The invention discloses an ethyl cellulose type calcium nitrite corrosion inhibitor and a preparation method thereof. The shape of the ethyl cellulose type calcium nitrite corrosion inhibitor is a capsule, the capsule comprises a capsule core and a coating; the ingredients of the capsule core comprise calcium nitrite, microcrystalline cellulose and Twin 80; and the coating is made from ethyl cellulose aqueous dispersion. According to the invention, the calcium nitrite microcapsule corrosion inhibitor coated by the ethyl cellulose aqueous dispersion has good stability, and the mass ratio of the capsule core material to the coating material is changed to guarantee controllable release speed, long validity period, good antirust effect and environmental friendliness for the microcapsule.
Description
[technical field]
The present invention relates to inorganic rust inhibitor, relate in particular to a kind of TKK 021 class calcium nitrite inhibiter and preparation method thereof.
[background technology]
Used one type of inorganic rust inhibitor the most widely is to mainly contain calcium nitrite on the engineering now.A large amount of research has just been done to calcium nitrite since the seventies in last century by U.S. Grace company, because it does not have tangible one time of negative impact for the rust inhibitor of main flow on the America and Japan market to concrete.
Calcium nitrite belongs to and directly mixes the type rust inhibitor, in use, directly calcium nitrite is incorporated into to stir in the concrete structure and gets final product.To its mechanism of action, the viewpoint basically identical of Chinese scholars.The chemical expression of its provide protection is following:
Fe
2++OH
-+NO
- 2＝NO+γ-FeOOH (1)
2Fe
2++2OH
-+2NO
- 2＝2NO+Fe
2O
3+H
2O (2)
For the explanation of mechanism, mainly have three kinds of viewpoint different: domestic scholars Mr. Hong Naifeng thinks that ferrous ion that nitrite anions and anodic reaction produce generates the γ-FeOOH with protective membrane and covers rebar surface and prevent that reinforcing bar from wrecking.Because villaumite when bringing out the destroying concrete structure of formation, the provide protection of calcium nitrite is vied each other in the corrosion of bringing out with villaumite, when calcium nitrite when just provide protection is in windward then reinforcing bar be able to protection; Koichi Soeda thinks that nitrite has generated Fe2O3 at rebar surface, and when film forming speed during greater than corrosion reaction speed, then reinforcing bar is able to protection; When T.A.Soylev thinks that NO-2 and Fe2+ film formation reaction speed are greater than the depolarisation effect of cl ions, form stable Fe2O3 passive film at model machine.
Comprehensive three kinds of sayings all are that the requirement nitrite ion forms passive film in time.Directly mix owing to adopt in the construction process, the shortcoming of calcium nitrite itself makes that wherein a part of calcium nitrite is wasted.Just so; Its incorporation is difficult to satisfy the balance between economy and the benefit; Though therefore mixing of calcium nitrite can be played certain retarding action to the reinforcement corrosion of concrete structure, comparatively limit to, lack a kind of maneuvering ability of environmental change to external world.
Calcium nitrite is used in the skeleton construction as the earliest rust inhibitor, within use in structure preceding 20 years, has still played comparatively positive effect for the inhibition of reinforcing bar.But also just along with the continuation of using, some shortcomings that people are come out to calcium nitrite have during use caused that people are in the self-examination of selecting on this type rust inhibitor.
Construction technology according to calcium nitrite is divided, and it belongs to directly mixes the type rust inhibitor, and in conjunction with some physico-chemical properties of calcium nitrite self, this construction technology causes its problem that exists in the use to mainly contain: one, oxidized easily; Nitrite ion is not because the valency of nitrogen element reaches peak, and chemical property is relatively active, is prone to oxidation by air and loses efficacy and become faint yellowly, causes hindering the forfeiture of rust effect; Two, cause environmental issue; Nitrite itself is prone to carcinogenic, and the constructional method of directly mixing can cause the loss of nitrite, thereby causes can't being solved by its a series of environmental issues of bringing out; Three, resistance rust inefficiency, calcium nitrite at concrete structure during one's term of military service, calcium nitrite is prone to dissolving, in use constantly runs off with the pore texture in the concrete, causes its resistance rust efficient not high.
[summary of the invention]
The technical problem that the present invention will solve provides that a kind of validity period is long, the resistance rust is effective, the TKK 021 class calcium nitrite inhibiter of environmental protection and preparation method thereof.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is; A kind of TKK 021 class calcium nitrite inhibiter, its form is a capsule, described capsule comprises capsule-core and dressing; The component of said capsule-core comprises calcium nitrite, Microcrystalline Cellulose and tween 80, and the material of said dressing is an Aquacoat.
Above-described TKK 021 class calcium nitrite inhibiter, described capsule-core is made up of following proportioning by weight:
Calcium nitrite 100;
Microcrystalline Cellulose 60-140;
Tween 80 6-14.
Above-described TKK 021 class calcium nitrite inhibiter, the weight ratio that constitutes capsular capsule-core and Aquacoat is 1: 0.25 to 1: 4.
Above-described TKK 021 class calcium nitrite inhibiter, the diameter of capsule-core is 0.3 millimeter to 0.5 millimeter, capsular diameter is 0.35 millimeter to 1.5 millimeters.
More than one said TKK 021 class calcium nitrite inhibiter preparing methods' technical scheme may further comprise the steps:
501) coating liquid preparation: take by weighing the coating liquid raw material by following weight part:
Aquacoat 100;
Water 34-50;
Aquacoat is diluted in water, stirs, process coating liquid;
502) spray coating: capsule-core is put into the cylinder of spray coating equipment, under the dressing pattern, with pump the fog nozzle of coating liquid through equipment is sprayed onto on the capsule-core of rolling, the weight ratio of dry-matter is 1: 0.25 to 1: 4 in capsule-core and the coating liquid;
503) drying: at temperature 30-40 ℃, under the force ventilated condition: in the cylinder at drying plant dry 10-20 minute, lower the temperature naturally then, dry.
Above-described preparation method comprises the capsule-core preparation process:
601) capsule-core preparation: take by weighing the capsule-core raw material by following weight part:
Calcium nitrite 100;
Microcrystalline Cellulose 60-140;
Tween 80 6-14;
Water 8.8-9.6;
With calcium nitrite and the two thorough mixing of Microcrystalline Cellulose, add tween 80 then earlier, add entry after stirring, water is evenly existed in mixture;
602) extrude take out thin: with the charging opening input of described mixture, extrude the core materials of rice noodles strip at extrusion equipment;
603) discharging is round as a ball: with described rice noodles strip core materials, pour the cylinder in the rolling circle equipment into, roll out the capsule-core particulate;
604) drying: capsule-core is rolled out in the cylinder of particulate drying plant, under the drying temperature 30-40 ℃ of force ventilated condition, carry out drying treatment.
Above-described preparation method, described spray coating equipment, extrusion equipment, rolling circle equipment and drying plant all are to extrude spheronizator, describedly extrude that spheronizator comprises the spray coating pattern, extrudes pattern, round as a ball pattern and drying mode.
The present invention has satisfactory stability property with the calcium nitrite microcapsule inhibiter that Aquacoat wraps up; The variation of the quality proportioning through core materials and coating material; The rate of release of microcapsule can be accomplished optimized controllable, has solved the calcium nitrite rust inhibitor effectively and has been prone to the defective that loss is prone to oxidation; So the validity period of TKK 021 class calcium nitrite inhibiter of the present invention is long, the resistance rust is effective, and environmental protection.
[embodiment]
Through embodiment the present invention is further set forth below:
One, the capsular preparation of TKK 021 class calcium nitrite inhibiter:
Each embodiment material mixture ratio of table 1. capsule-core
Wherein: the function phase composition of calcium nitrite (emerging the chemical industry Group Co.,Ltd in Hubei, emerging dealing out the cards) inhibiter.
Microcrystalline Cellulose (mountains and rivers, Anhui pharmaceutical excipient limited-liability company, mountains and rivers board) is as filler and thickening material.
Tween 80 (Guangdong, Guangdong emigrant's reagent plastics ltd, Guangdong emigrant's board) is as dispersion agent.
Water (pure water or tap water) is as solvent.
Each embodiment material mixture ratio of table 2. dressing
Wherein: Aquacoat (Shanghai Colorcon Coating Technology Co., Ltd, Ka Lekang board): as film forming material.
Water (pure water or tap water) is as solvent.
TKK 021 class calcium nitrite inhibiter capsule embodiment 1:
Equipment adopts extrudes spheronizator (Xinyi, Shenzhen trick ltd, LTAES 380 types)
1. capsule-core preparation: according to the weight proportion of the V capsule-core in the table 1,, mix the back and add tween 80 earlier with calcium nitrite and the two thorough mixing of Microcrystalline Cellulose, rub with the hands mix evenly after gradation adding pure water again, pure water can evenly be existed in mixture.
2. extrude and take out carefully: open and extrude spheronizator, the pattern of extruding of starting outfit feeds intake at charging opening, the cooling water circulation pattern of starting outfit, and preventing to squeeze a tube generation excessive temperature influences discharging.
3. discharging is round as a ball: the core materials that collects the rice noodles strip of extruding with pallet; Pour the cylinder in the equipment into; The round as a ball pattern of starting outfit; (rotating speed is controlled at 700～1100r/min), constantly takes out an amount of sample during rotation and comes out to observe, till in sample, not occurring conjuncted capsule-core or capsule-core particulate basically and not cohering each other to regulate round as a ball slewing rate.After the taking-up capsule-core particulate is put into cylinder once more, start drying mode, regulate drying temperature (drying temperature is controlled at 30～40 ℃) and air intake speed, the capsule-core material is carried out drying treatment, obtain the capsule-core finished product, the diameter of capsule-core finished product is the 0.3-0.5 millimeter.
5. coating liquid preparation: by the weight ratio of capsule-core and Aquacoat is to take by weighing coating material at 1: 0.25, and the coating material weight proportion is pressed the weight proportion of the I dressing in the table 2.Aquacoat and pure water are proportionally diluted.
6. spray coating: the capsule-core particle that drying is good is put into the cylinder of extruding spheronizator once more, starts the dressing pattern, connects fog nozzle and coating liquid with peristaltic pump, adjustment hydrojet speed (air blast flux 2200L/h; Spray pressure 0.2Mpa is till coating liquid has sprayed fully.
According to the drying parameter in the step 3, behind the microcapsule after drying (general 15 minutes) after the spraying, spread the cooling of giving free rein to after the taking-up out, dry and obtain capsule finished product.
TKK 021 class calcium nitrite inhibiter capsule embodiment 2:
1, capsule-core preparation: according to the weight proportion of III capsule-core in the table 1,
2, coating liquid preparation: the weight proportion of III dressing in the option table 2 is to take by weighing coating material at 1: 1 by the weight ratio of capsule-core and Aquacoat.
Other process steps, parameter and equipment are with embodiment 1.
TKK 021 class calcium nitrite inhibiter capsule embodiment 3:
1, capsule-core preparation: according to the weight proportion of I capsule-core in the table 1,
2, coating liquid preparation: the weight proportion of V dressing in the option table 2 is to take by weighing coating material at 1: 4 by the weight ratio of capsule-core and coating material dry-matter.
Other process steps, parameter and equipment are with embodiment 1.
Two, the capsular particle size range of TKK 021 class calcium nitrite inhibiter:
Through the change of size of the prepared TKK 021 class calcium nitrite microcapsule of present method from 350 μ m (corresponding core materials: the mass ratio of Aquacoat=1: 0.25) to 1000 μ m (corresponding core materials: the mass ratio of Aquacoat=1: 4)
Four, TKK 021 class calcium nitrite inhibiter capsule microscopic appearance
Utilize opticmicroscope that the form of microcapsule is taken (seeing Fig. 1 and Fig. 2); Observe to find the microcapsule size uniform particles, shape presents the ellipsoid shape, and has that some are concavo-convex; Analyze its major cause, mainly be at the capsule-core particle round as a ball and high-pressure fog process medium speed and not exclusively evenly due to.Consider the irregularities of concrete material internal pore structure, so the regularity of its form does not have material impact to its use.
Five, capsular stability of TKK 021 class calcium nitrite inhibiter and rate of release
Get the beaker of 200ml, measure the 200ml ultrapure water with the 250ml graduated cylinder and be poured in the beaker, weigh with scale calcium nitrite powder and each 10g of calcium nitrite microcapsule put into beaker and observe its stability.Under the protection of Aquacoat dressing, microcapsule still present graininess in the aqueous solution, and calcium nitrite is by thorough dissolving.
Get the beaker of 200ml, measure the 200ml ultrapure water with the 250ml graduated cylinder and be poured in the beaker, each 10g of calcium nitrite microcapsule of weigh with scale calcium nitrite powder and different embodiment preparations puts into beaker; With 3 hours, 6 hours, 12 hours, 24 hours, 48 hours be the concentration of test soln reference time, calculate the content of calcium nitrite in the 200ml solution:
Content (the unit: gram) of calcium nitrite in the table 3.200ml solution
The present invention is a kind of method of utilizing the spray drying method for preparation microcapsule.Its cardinal principle be utilize high-pressure sprayer give capsule-core particle surface in cylinder high speed running spray can bonding capsule-core particle surface liquid high polymeric solution, spray that the back makes the high polymer solvent evaporation through high temperature and a kind of microcapsule technology of preparing of forming high-polymer membrane on its surface.The present invention utilizes the diluent of Aquacoat to be sprayed at this novel rust inhibitor material of calcium nitrite capsule that the solid particles surface that is made into calcium nitrite and Microcrystalline Cellulose prepares the acrylic resin parcel just.
Experimental result can be found out; The calcium nitrite microcapsule inhibiter that wraps up with Aquacoat has satisfactory stability property; And along with the variation of the quality proportioning of core materials, coating material; The rate of release of microcapsule can be accomplished optimized controllable, is prone to the purpose that loss is prone to oxidation thereby reach effective solution calcium nitrite rust inhibitor.
Beneficial effect of the present invention is following:
(1) utilize the high-pressure spray-drying principle to form one deck barrier film on the calcium nitrite surface, calcium nitrite is able to protection, is implemented in the construction technology of directly mixing in the whipping process, avoids the influence of external environment to calcium nitrite;
(2) the awkward water-soluble material of barrier film constitutes, and barrier film can tightly wrap calcium nitrite, overcomes the shortcoming that it runs off under aqueous solution state easily;
(3) the successful microcapsule of the preparation thickness of can experimental effect adjusting cyst wall is realized the intelligent control to capsule-core; Make the calcium nitrite microcapsule adjust the speed of its release, reach to the variation of external environment and the purpose of mobile reactant through the variation of the external stimulus environment estimated.
Claims (7)
1. TKK 021 class calcium nitrite inhibiter; It is characterized in that its form is a capsule, described capsule comprises capsule-core and dressing; The component of said capsule-core comprises calcium nitrite, Microcrystalline Cellulose and tween 80, and the material of said dressing is an Aquacoat.
2. TKK 021 class calcium nitrite inhibiter according to claim 1 is characterized in that described capsule-core is made up of following proportioning by weight:
Calcium nitrite 100;
Microcrystalline Cellulose 60-140;
Tween 80 6-14.
3. TKK 021 class calcium nitrite inhibiter according to claim 1 is characterized in that the weight ratio that constitutes capsular capsule-core and Aquacoat is 1: 0.25 to 1: 4.
4. TKK 021 class calcium nitrite inhibiter according to claim 1 is characterized in that the diameter of capsule-core is 0.3 millimeter to 0.5 millimeter, and capsular diameter is 0.35 millimeter to 1.5 millimeters.
5. the preparation method of the said TKK 021 class of claim 1 a calcium nitrite inhibiter is characterized in that, may further comprise the steps:
501) coating liquid preparation: take by weighing the coating liquid raw material by following weight part:
Aquacoat 100;
Water 34-50;
Aquacoat is diluted in water, stirs, process coating liquid;
502) spray coating: the cylinder of capsule-core being put into spray coating equipment; Under the dressing pattern; With pump the fog nozzle of coating liquid through equipment is sprayed onto on the capsule-core of rolling, the weight ratio of Aquacoat is 1: 0.25 to 1: 4 in capsule-core and the coating liquid;
503) drying: at temperature 30-40 ℃, under the force ventilated condition: in the cylinder at drying plant dry 10-20 minute, lower the temperature naturally then, dry.
6. preparation method according to claim 7 is characterized in that, comprises the capsule-core preparation process:
601) capsule-core preparation: take by weighing the capsule-core raw material by following weight part:
Calcium nitrite 100;
Microcrystalline Cellulose 60-140;
Tween 80 6-14;
Water 8.8-9.6;
With calcium nitrite and the two thorough mixing of Microcrystalline Cellulose, add tween 80 then earlier, add entry after stirring, water is evenly existed in mixture;
602) extrude take out thin: with the charging opening input of described mixture, extrude the core materials of rice noodles strip at extrusion equipment;
603) discharging is round as a ball: with described rice noodles strip core materials, pour the cylinder in the rolling circle equipment into, roll out the capsule-core particulate;
604) drying: capsule-core is rolled out in the cylinder of particulate drying plant, under the drying temperature 30-40 ℃ of force ventilated condition, carry out drying treatment.
7. according to claim 5 or 6 described preparing methods; It is characterized in that; Described spray coating equipment, extrusion equipment, rolling circle equipment and drying plant are all to extrude spheronizator, describedly extrude that spheronizator comprises the spray coating pattern, extrudes pattern, round as a ball pattern and drying mode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110378772.5A CN102517587B (en) | 2011-11-25 | 2011-11-25 | A kind of ethyl cellulose type calcium nitrite corrosion inhibitor and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110378772.5A CN102517587B (en) | 2011-11-25 | 2011-11-25 | A kind of ethyl cellulose type calcium nitrite corrosion inhibitor and preparation method thereof |
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| CN102517587A true CN102517587A (en) | 2012-06-27 |
| CN102517587B CN102517587B (en) | 2015-12-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016155613A1 (en) * | 2015-03-31 | 2016-10-06 | 深圳大学 | Microcapsule for self-repairing concrete and preparation method thereof, and self-repairing concrete and preparation method thereof |
| CN106431069A (en) * | 2016-09-09 | 2017-02-22 | 深圳大学 | Slowly released type anti-rust microcapsules applied to steel reinforced concrete and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA830389A (en) * | 1969-12-23 | C. Cessna John | Encapsulated corrosion inhibitor |
-
2011
- 2011-11-25 CN CN201110378772.5A patent/CN102517587B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA830389A (en) * | 1969-12-23 | C. Cessna John | Encapsulated corrosion inhibitor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016155613A1 (en) * | 2015-03-31 | 2016-10-06 | 深圳大学 | Microcapsule for self-repairing concrete and preparation method thereof, and self-repairing concrete and preparation method thereof |
| CN106431069A (en) * | 2016-09-09 | 2017-02-22 | 深圳大学 | Slowly released type anti-rust microcapsules applied to steel reinforced concrete and preparation method thereof |
| CN106431069B (en) * | 2016-09-09 | 2019-06-25 | 深圳大学 | A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete |
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|---|---|
| CN102517587B (en) | 2015-12-16 |
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