CN106431069B - A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete - Google Patents
A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete Download PDFInfo
- Publication number
- CN106431069B CN106431069B CN201610814609.1A CN201610814609A CN106431069B CN 106431069 B CN106431069 B CN 106431069B CN 201610814609 A CN201610814609 A CN 201610814609A CN 106431069 B CN106431069 B CN 106431069B
- Authority
- CN
- China
- Prior art keywords
- release
- microcapsules
- core material
- corrosion inhibitor
- slow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1048—Polysaccharides, e.g. cellulose, or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The slow-release resistance rust microcapsules and preparation method thereof that the present invention provides a kind of applied to armored concrete, the slow-release resistance rust microcapsules applied to armored concrete, it includes core material and wall material, it is characterized by: the core material includes inorganic corrosion inhibitor and auxiliary material, the wall material includes the high molecular material for controlling corrosion inhibitor release；The component and its parts by weight that the core material includes are as follows: 100 parts of inorganic corrosion inhibitor, 90 ~ 110 parts of microcrystalline cellulose, 2 ~ 4 parts of hydroxypropyl methyl cellulose.Slow-release applied to armored concrete of the invention hinders the smaller of rust microcapsules, and size modification scope is wider, and carrying drug ratio is higher；Its wall material thickness can regulate and control according to the requirement to rate of release and period, achieve the purpose that control release；Have the characteristics that preparation flow is simple, utilization rate of raw materials is high, carrying drug ratio is high, size modification scope is wider, the Release of core material period is long, rate of release is controllable.
Description
Technical field
The invention belongs to field of material technology, it is related to a kind of reinforcing bar resistance rust microcapsules, more particularly to a kind of applied to reinforcing bar
Slow-release resistance rust microcapsules of concrete and preparation method thereof.
Background technique
In the building of strand, due to the characteristic of seawater, make the reinforcing bar in concrete that electrochemical corrosion easily occur in the seawater,
The corrosion of reinforcing bar will lead to the decline of reinforced concrete structure material property and even fail.It is anti-in structural metallic materials under conventional environment
Corrosion aspect expenditure account for about the 2%~4% of totle drilling cost, and in the more complex marine environment of corrosive environment then up to 10%~
30%.Therefore, it develops service efficiency height and low-cost concrete corrosion resistant agent becomes the hot spot studied both at home and abroad.
Reinforcing steel bar corrosion inhibitor is the chemical substance for having obvious retarding action to reinforcement corrosion, is typically directly incorporated into concrete
Or coating is carried out in reinforced concrete surface and plays the role of hindering rust.Traditional inorganic corrosion inhibitor has excellent resistance rust effect, mesh
Before some realization industrialization such as calcium nitrite etc..But inorganic corrosion inhibitor the disadvantages of there are higher toxicity, carcinogenicity, and mixed
It is easily outflowed with water in solidifying soil.Inorganic corrosion inhibitor is coated with high molecular material, makes its microencapsulation, is to reduce its use
Amount reduces toxicity and improves the effective means of corrosion inhibitor service efficiency.
The prior art generally uses extrusion spheronization granulation-coating method to prepare microcapsules, but this method is prepared
The size of microcapsules is larger, in 400um or more, cannot reduce capsule size as needed, and microcapsule preparation process is more
Complexity, technique is more demanding when core material when extrusion spheronization, and resulting microcapsules carrying drug ratio is relatively low, and usually only 20% is left
It is right.Besides the method for using blended melting to squeeze out inorganic corrosion inhibitor and high molecular material, available with certain slow
It releases the blended particles of effect, but often due to temperature is higher when processing, is not suitable for the poor core material of thermal stability, and the core having
Material has stronger destruction to equipment at high temperature.
Summary of the invention
Against the above technical problems, the invention discloses a kind of slow-releases applied to armored concrete to hinder rust microcapsules,
The capsule size is small, and preparation flow is simple, had good sustained release effect, and Release of core material controllable-rate.
In this regard, the technical solution adopted by the present invention are as follows:
A kind of slow-release resistance rust microcapsules applied to armored concrete, including core material and wall material, the core material include nothing
Machine corrosion inhibitor and auxiliary material, the wall material include the high molecular material for controlling corrosion inhibitor release；Component that the core material includes and its
Parts by weight are as follows: 100 parts of inorganic corrosion inhibitor, 90~110 parts of microcrystalline cellulose, 2~4 parts of hydroxypropyl methyl cellulose.Wherein, institute
Microcrystalline cellulose is stated as carrier, this technical solution directly directly mixes carrier and corrosion inhibitor as core material, improves micro- glue
The content of corrosion inhibitor in capsule has preferably resistance rust effect in lesser size.Wall material is wrapped in the outer surface of core material simultaneously,
The rate of release that core material in microcapsules can be controlled by the coating material of wall material, achievees the purpose that long-term slow release.The control
The high molecular material of corrosion inhibitor release processed is polymer not soluble in water.Environment of the practical armored concrete in sea water solution is wanted
More complicated than simulated seawater concrete solution is more, and the decline of environment pH value is faster, therefore slow-release resistance rust microcapsules are in reality
Rate of release in the application of border can be slower, and deenergized period is longer than in simulated seawater concrete solution.Using this technical side
Case, obtained slow-release resistance rust capsule size is small, and carrying drug ratio is higher, can be usually reached 30% or so.With coarse sand and cement one
It rises and is added in armored concrete, the loss of inorganic corrosion inhibitor when in use can be greatly reduced, improve service efficiency.
As a further improvement of the present invention, the core material and the mass ratio of wall material are 1:(0.1-0.4).Using this technology
Scheme obtains the microcapsules with slow release effect, by controlling the ratio of core material and wall material, the release speed of adjustable core material
Rate realizes different slow release speeds；This technical solution improves the content of corrosion inhibitor in microcapsules, and corrosion inhibitor mass content exists
30% or so, higher than the content of the prior art.And the technical program can adjust as needed capsule size 0.15~
0.5mm, size range is wider, can meet the needs of different application environment.By being 1 by the mass ratio control of core material and wall material:
(0.1-0.4) makes it have suitable slow release speed to control the thickness of wall material, plays preferably resistance rust effect.
As a further improvement of the present invention, the slow-release resistance rust microcapsules are elliposoidal, the core material before being coated
Diameter is 0.1~0.4mm, and the diameter of microcapsules is 0.15~0.5mm after coating.
Preferably, the diameter of the core material is 0.1~0.25mm before being coated, and the diameter of microcapsules is 0.15- after coating
0.35mm。
As a further improvement of the present invention, component and its parts by weight that the core material includes are as follows: inorganic corrosion inhibitor 100
Part, 95~105 parts of microcrystalline cellulose, 2.5~3 parts of hydroxypropyl methyl cellulose.
As a further improvement of the present invention, the inorganic corrosion inhibitor include calcium nitrite, sodium monofluorophosphate, cerous nitrate,
At least one of calcium hydroxide and barium hydroxide；The auxiliary material includes thickener and adhesive.
As a further improvement of the present invention, the high molecular material of the control corrosion inhibitor release is ethyl cellulose, gathers
At least one of styrene, polycarbonate or polymethyl methacrylate, but it is not limited only to several macromolecules mentioned above
Material.
As a further improvement of the present invention, the slow-release resistance rust microcapsules applied to armored concrete are using following
Step is prepared:
Step S1: centrifugal process prepares core material；
It will be added in centrifugation apparatus after inorganic corrosion inhibitor and auxiliary materials and mixing, successively open air blast, blower speed 400
~600r/min, rotary speed are 400~600r/min, open peristaltic pump feed flow, and wriggling revolution speed is 10~20r/min, to
Material closes peristaltic pump when in pot being in cotton-shaped flowing, continues to rotate, and polishes, takes when the size of particle and hardness reach requirement
Core material is made in drying out.Different preparation parameter correspondences obtain different Microcapsules Size sizes, preferred parameter are as follows: air blast
Flow is 400~500r/min, and rotary speed is 500~600r/min, and liquid supply speed is 10~15r/min.
Step S2: coating solution is prepared；
By it is described control corrosion inhibitor release high molecular material be added in organic solvent, magnetic stirring apparatus heating and
Transparent uniform coating solution is made under stirring；
Step S3: fluidized bed coating；
Core material is placed in fluidized bed, under coating mode, adjusts 800~1300rpm of rotation speed of fan and aspiration pressure 0.9
~0.12mpa, and start to preheat, adjusting inlet air temperature makes temperature of charge at 30~40 DEG C, and it opens peristaltic pump and starts hydrojet coating,
Coating solution stops coating and drying after having sprayed.Wherein, the size of the controllable microcapsules wall thickness of the amount of coating solution, coating liquid measure are got over
More, microcapsules wall thickness is bigger, and microcapsules coating front and back diameter increase is more.
It adopts this technical solution, obtains the microcapsules with slow release effect, it, can be with by changing the thickness and type of wall material
The rate of release for adjusting core material, achievees the effect that sustained release；And with preparation flow is simple, utilization rate of raw materials is high, Release of core material
The features such as period is long, rate of release is controllable.And this technical solution is of less demanding to core material, as long as powder core material can be realized
Centrifugal granulator does not need prior wiring solution-forming, easy to operate.
There are the resistance rust microcapsules of slow release effect using the preparation of the method for centrifugal granulator and fluidized bed coating, there is preparation stream
The features such as journey is simple, utilization rate of raw materials is high, the Release of core material period is long, size modification scope is wider, rate of release is controllable, can be with
Overcome the inorganic corrosion inhibitor of tradition using when additive amount is big, have the shortcomings that higher toxicity, carcinogenicity, release are too fast.Using this system
The size of the microcapsules that Preparation Method obtains, core material can be carried out by changing centrifugal basket disk rotating speed, liquid supply speed, blow rate required etc.
Adjustment, so that Release of core material period, rate of release are controllable.Core material particles after general drying are irregular elliposoidal, directly
Diameter is between 0.1-0.4mm；The thickness of wall material can be adjusted by changing the weight of high molecular material in coating solution, be completed
The surface of microcapsules becomes smooth and fine and close after coating, is in ellipsoid, diameter is between 0.15-0.5mm.Capsule size range
Increase, is also applied for the poor core material of thermal stability.
As a further improvement of the present invention, described in the coating solution control corrosion inhibitor release high molecular material with have
The mass ratio of solvent is 1:(10~16).It adopts this technical solution, is changed by the weight of high molecular material in control coating solution
Become the thickness of wall material, the rate of release of adjustable core material realizes different slow release speeds.
As a further improvement of the present invention, the high molecular material of the control corrosion inhibitor release is polystyrene or poly- first
Base methyl acrylate, the organic solvent are ethyl acetate, the polystyrene or polymethyl methacrylate and ethyl acetate
Mass ratio be 1:(10~15)；Alternatively, the high molecular material of the control corrosion inhibitor release is ethyl cellulose, the ethyl
The mass ratio of cellulose and ethyl acetate is 1:(12~15)；Alternatively, the high molecular material of the control corrosion inhibitor release is poly-
The mass ratio of carbonic ester, the polycarbonate and ethyl acetate is 1:(13~16).It adopts this technical solution, is coated by control
The weight of high molecular material in liquid, controls the thickness of wall material, to adjust the rate of release of core material, and achievees the effect that sustained release.
As a further improvement of the present invention, in step S1, the blower speed is 400~500r/min, and turntable turns
Speed is 500~600r/min, and wriggling revolution speed is 10~15r/min.It adopts this technical solution, the grain of obtained resistance rust microcapsules
Diameter is smaller, and carrying drug ratio is higher.
The invention also discloses the micro- glue of slow-release resistance rust for being applied to armored concrete described in a kind of any one as above
The preparation method of capsule, comprising the following steps:
Step S1: centrifugal process prepares core material；
It will be added in centrifugation apparatus after inorganic corrosion inhibitor and auxiliary materials and mixing, successively open air blast, blower speed 400
~600r/min, rotary speed are 400~600r/min, open peristaltic pump feed flow, and wriggling revolution speed is 10~20r/min, to
Material closes peristaltic pump when in pot being in cotton-shaped flowing, continues to rotate, and polishes, takes when the size of particle and hardness reach requirement
Core material is made in drying out.Different preparation parameter correspondences obtain different Microcapsules Size sizes, preferred parameter are as follows: air blast
Flow is 400~500r/min, and rotary speed is 500~600r/min, and liquid supply speed is 10~15r/min；
Step S2: coating solution is prepared；
By it is described control corrosion inhibitor release high molecular material be added in organic solvent, magnetic stirring apparatus heating and
Transparent uniform coating solution is made under stirring；
Step S3: fluidized bed coating；
Core material is placed in fluidized bed, under coating mode, adjusts 800~1300rpm of rotation speed of fan and aspiration pressure 0.9
~0.12mpa, and start to preheat, adjusting inlet air temperature makes temperature of charge at 30~40 DEG C, and it opens peristaltic pump and starts hydrojet coating,
Coating solution stops coating and drying after having sprayed.
It adopts this technical solution, compared with prior art, the particle size range of obtained resistance rust microcapsules is wider, can achieve
Between 150~500um, the partial size that other available preparation methods are difficult to realize is less than the microcapsules corrosion inhibitor of 200um.
As a further improvement of the present invention, described in the coating solution control corrosion inhibitor release high molecular material with have
The mass ratio of solvent is 1:(10~16).Different high molecular materials corresponds to different organic solvent mass ratioes, preferred matter
Amount is than being 1:12~15.
As a further improvement of the present invention, the high molecular material of the control corrosion inhibitor release is polystyrene or poly- first
Base methyl acrylate, the organic solvent are ethyl acetate, the polystyrene or polymethyl methacrylate and ethyl acetate
Mass ratio be 1:(10~15)；Alternatively, the high molecular material of the control corrosion inhibitor release is ethyl cellulose, the ethyl
The mass ratio of cellulose and ethyl acetate is 1:(12~15)；Alternatively, the high molecular material of the control corrosion inhibitor release is poly-
The mass ratio of carbonic ester, the polycarbonate and ethyl acetate is 1:(13~16).
As a further improvement of the present invention, in step S1, the blower speed is 400~500r/min, and turntable turns
Speed is 500~600r/min, and wriggling revolution speed is 10~15r/min.It adopts this technical solution, the grain of obtained resistance rust microcapsules
Diameter is smaller, and carrying drug ratio is higher.
Compared with prior art, the invention has the benefit that
First, a kind of slow-release resistance rust microcapsules applied to armored concrete of the present invention, are based on simulated seawater coagulation
In native solution triggering and can long-term sustained release microcapsules, be different from traditional microcapsules, microcapsules according to the present invention,
Wall material thickness can regulate and control according to the requirement to rate of release and period, achieve the purpose that control release, compare existing
The microcapsules that patent extrusion spheronization-coating method obtains, size range is generally in 300~500um, and carrying drug ratio is 20% or so；This
The size for inventing obtained microcapsules can be reduced to 150um, and size modification scope is wider, and between 0.15~0.5mm, carrying drug ratio is more
Height can reach 40% or more, significantly larger than the 20% of the prior art.
Second, slow-release type microcapsule corrosion inhibitor of the present invention is with preparation flow is simple, utilization rate of raw materials is high, carrying drug ratio
The features such as height, size modification scope are wider, the Release of core material period is long, rate of release is controllable.
Detailed description of the invention
Fig. 1 is that 1 slow-release of embodiment of the present invention resistance rust microcapsules are coated after preceding and coating under a scanning electron microscope
Microscopic appearance figure.
Fig. 2 is slow-release resistance rust microcapsules under a scanning electron microscope microcosmic in the embodiment of the present invention 2 and embodiment 3
Pattern comparison diagram.
Fig. 3 is the slow-release resistance rust microcapsules of the different weight gains of the embodiment of the present invention 1 in simulated seawater concrete solution core
The curve graph of material rate of release.
Fig. 4 be the mass ratio of 1 core material of the embodiment of the present invention and wall material be 1:0.1 slow-release resistance rust microcapsules in simulation sea
60 days microscopic appearance figures are impregnated in water coagulation soil solution.
Fig. 5 be the mass ratio of 1 core material of the embodiment of the present invention and wall material be 1:0.2 slow-release resistance rust microcapsules in simulation sea
60 days microscopic appearance figures are impregnated in water coagulation soil solution.
Fig. 6 be the mass ratio of 1 core material of the embodiment of the present invention and wall material be 1:0.3 slow-release resistance rust microcapsules in simulation sea
60 days microscopic appearance figures are impregnated in water coagulation soil solution.
Specific embodiment
With reference to the accompanying drawing, preferably embodiment of the invention is described in further detail.
The preparation method of slow-release resistance rust microcapsules of the present invention is broadly divided into two steps of centrifugal granulator and fluidized bed coating,
The size of Microcapsules Size can be adjusted by changing the technological parameter of centrifugal granulating, and the wall material thickness of microcapsules can pass through
The ratio of core material wall material adjusts when changing fluidized bed coating.It, can be according to practical need using the resistance rust microcapsules of this method preparation
Suitable macromolecule wall material and inorganic corrosion inhibitor core material are selected, and adjusts rate of release by changing wall material thickness, is reached
The effect of sustained release.
The present invention is further elaborated below by embodiment:
One, the embodiment applied to the preparation method of the slow-release resistance rust microcapsules of armored concrete, according to Tables 1 and 2
In formula prepare core material and coating solution raw material.
Each embodiment raw material mass mixture ratio of 1 core material of table
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Sodium monofluorophosphate | 100 | --- | --- | --- | --- |
| Calcium nitrite | --- | 100 | --- | --- | --- |
| Cerous nitrate | --- | --- | 100 | --- | --- |
| Calcium hydroxide | --- | --- | --- | 100 | --- |
| Barium hydroxide | --- | --- | --- | --- | 100 |
| Microcrystalline cellulose | 90 | 95 | 100 | 105 | 110 |
| Deionized water | 110 | 120 | 130 | 120 | 130 |
| Hypromellose | 2 | 3 | 4 | 3 | 4 |
Wherein:
Sodium monofluorophosphate (Wuxi Rui Yuan Chemical Co., Ltd. analyzes pure) is inorganic corrosion inhibitor；
Calcium nitrite (Shanghai prosperity Chemical Co., Ltd. analyzes pure) is inorganic corrosion inhibitor；
Cerous nitrate (Xilong Chemical Co., Ltd analyzes pure) is inorganic corrosion inhibitor；
Calcium hydroxide (Xilong Chemical Co., Ltd analyzes pure) is inorganic corrosion inhibitor；
Barium hydroxide (Xilong Chemical Co., Ltd analyzes pure) is inorganic corrosion inhibitor；
Microcrystalline cellulose (the grand Science and Technology Ltd. of Hubei good luck) is used as thickener；
Hydroxypropyl methyl cellulose (Shijiazhuang Hong Lai cellulose Co., Ltd) is used as adhesive.
Each embodiment coating solution raw material mass mixture ratio of table 2
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Ethyl cellulose | 100 | --- | --- | --- | 100 |
| Polystyrene | --- | 100 | --- | --- | --- |
| Polycarbonate | --- | --- | 100 | --- | --- |
| Polymethyl methacrylate | --- | --- | --- | 100 | --- |
| Ethyl acetate | 1200 | 1300 | 1350 | 1400 | 1500 |
Wherein:
Ethyl cellulose (Guangzhou Dao Jun Chemical Industry Science Co., Ltd), as the macromolecule material that can control corrosion inhibitor release
Material；
Polystyrene (Shanghai Sai Ke petrochemical industry Co., Ltd), as the macromolecule material that can control corrosion inhibitor release
Material；
Polycarbonate (Shanghai Sai Ke petrochemical industry Co., Ltd), as the macromolecule material that can control corrosion inhibitor release
Material；
Polymethyl methacrylate (Shanghai Sai Ke petrochemical industry Co., Ltd), as the height that can control corrosion inhibitor release
Molecular material；
Ethyl acetate (Xi Long Chemical Co., Ltd.) is used as solvent；
Embodiment 1
Ethyl cellulose/sodium monofluorophosphate resistance rust microcapsules preparation method, comprising the following steps:
1) centrifugal process prepares core material: being added to centrifugation after 1000g sodium monofluorophosphate and auxiliary material are mixed in the ratio of table 1 and sets
In standby, air blast is successively opened, blower speed 400r/min, rotary speed 600r/min open peristaltic pump feed flow, and peristaltic pump turns
Fast 10r/min, liquid supply rate 300ml, when material in pot be in cotton-shaped flowing when close peristaltic pump, continue to rotate, polish, to
The size and hardness of grain take out drying when reaching requirement, and core material is made.
2) coating solution is prepared: ethyl cellulose being added in ethyl acetate by the proportion of table 2, in adding for magnetic stirring apparatus
Transparent uniform coating solution is made under heat and stirring.
3) fluidized bed coating: 200g core material is placed in fluidized bed, and under coating mode, adjusting rotation speed of fan is
800rpm, aspiration pressure 0.9mpa, and start to preheat, adjusting inlet air temperature makes temperature of charge stablize 30~40 DEG C, opens compacted
Dynamic to pump and adjust wriggling revolution speed as 15r/min, the quality of wall material ethyl cellulose is 20g in coating solution, after coating solution has sprayed
Stop coating, is taken out after 10-20 minutes dry.
Quality by changing wall material in coating solution can obtain the microcapsules of different wall material weight gains, finally obtained micro- glue
The partial size of capsule is mainly distributed on 0.15-0.25mm, carrying drug ratio 47.3%.
Embodiment 2
The preparation methods of polystyrene/calcium nitrite resistance rust microcapsules the following steps are included:
1) centrifugal process prepares core material: being added to centrifugation apparatus after 1000g calcium nitrite and auxiliary material are mixed in the ratio of table 1
In, air blast is successively opened, blower speed 400r/min, rotary speed 500r/min open peristaltic pump feed flow, wriggling revolution speed
10r/min, liquid supply rate 400ml close peristaltic pump when material is in cotton-shaped flowing in pot, continue to rotate, polish, to particle
Size and hardness take out drying when reaching requirement, core material is made.
2) coating solution is prepared: polystyrene being added in ethyl acetate by the proportion of table 2, in the heating of magnetic stirring apparatus
With transparent uniform coating solution is made under stirring.
3) fluidized bed coating: 200g core material is placed in fluidized bed, and under coating mode, adjusting rotation speed of fan is
1300rpm, aspiration pressure 0.12mpa, and start to preheat, adjusting inlet air temperature makes temperature of charge stabilize to 30~40 DEG C, opens
It opens peristaltic pump and adjusts wriggling revolution speed 20r/min, the quality of wall material polystyrene is 40g in coating solution, after coating solution has sprayed
Stop coating, is taken out after 10-20 minutes dry, Microcapsules Size obtained is mainly distributed on 0.2-0.3mm, and carrying drug ratio is
42.1%.
Embodiment 3
Polycarbonate/cerous nitrate resistance rust microcapsules preparation method, comprising the following steps:
1) centrifugal process prepares core material: being added in centrifugation apparatus after 1000g cerous nitrate is mixed in the ratio of table 1, successively
Air blast is opened, blower speed 500r/min, rotary speed 400r/min open peristaltic pump feed flow, wriggling revolution speed 20r/
Min, liquid supply rate 400ml close peristaltic pump when material is in cotton-shaped flowing in pot, continue to rotate, polish, to the big of particle
Small and hardness takes out drying when reaching requirement, and core material is made.
2) coating solution is prepared: polycarbonate being added in ethyl acetate by the proportion of table 2, in the heating of magnetic stirring apparatus
With transparent uniform coating solution is made under stirring.
3) fluidized bed coating: 200g core material is placed in fluidized bed, and under coating mode, adjusting rotation speed of fan is
1000rpm, aspiration pressure 0.10mpa, and start to preheat, adjusting inlet air temperature stablizes temperature of charge at 30~40 DEG C, opens
It opens peristaltic pump and adjusts wriggling revolution speed 10r/min, the quality of wall material polycarbonate is 80g in coating solution, after coating solution has sprayed
Stop coating, is taken out after 10-20 minutes dry, Microcapsules Size obtained is mainly distributed on 0.35-0.5mm, and carrying drug ratio is
35.1%.
Embodiment 4
Polymethyl methacrylate/calcium hydroxide resistance rust microcapsules preparation method, comprising the following steps:
1) centrifugal process prepares core material: being added to centrifugation apparatus after 1000g calcium hydroxide and auxiliary material are mixed in the ratio of table 1
In, air blast is successively opened, blower speed 600r/min, rotary speed 400r/min open peristaltic pump feed flow, wriggling revolution speed
10r/min, liquid supply rate 350ml close peristaltic pump when material is in cotton-shaped flowing in pot, continue to rotate, polish, to particle
Size and hardness take out drying when reaching requirement, core material is made.
2) coating solution is prepared: the proportion of polymethyl methacrylate being added in ethyl acetate, in magnetic stirring apparatus
Transparent uniform coating solution is made under heating and stirring.
3) fluidized bed coating: 200g core material is placed in fluidized bed, and under coating mode, adjusting rotation speed of fan is
1200rpm and aspiration pressure are 0.11mpa, and start to preheat, and adjusting inlet air temperature makes temperature of charge stabilize to 30~40 DEG C, are opened
Opening peristaltic pump and adjusting wriggling revolution speed is 15r/min, and the quality of wall material polymethyl methacrylate is 40g, packet in coating solution
Clothing liquid stops coating after having sprayed, drying 10~take out after twenty minutes, Microcapsules Size obtained is mainly distributed on 0.2~0.3mm,
Carrying drug ratio is 40.1%.
Embodiment 5
Ethyl cellulose/barium hydroxide resistance rust microcapsules preparation method:
1) centrifugal process prepares core material: being added to centrifugation apparatus after 1000g barium hydroxide and auxiliary material are mixed in the ratio of table 1
In, air blast is successively opened, blower speed 500r/min, rotary speed 600r/min open peristaltic pump feed flow, wriggling revolution speed
15r/min, liquid supply rate 300ml close peristaltic pump when material is in cotton-shaped flowing in pot, continue to rotate, polish, to particle
Size and hardness take out drying when reaching requirement, core material is made.
2) coating solution is prepared: ethyl cellulose being added in ethyl acetate by the proportion of table 2, in adding for magnetic stirring apparatus
Transparent uniform coating solution is made under heat and stirring.
3) fluidized bed coating: 200g core material is placed in fluidized bed, and under coating mode, adjusting rotation speed of fan is
1300rpm, aspiration pressure 0.12mpa, and start to preheat, adjusting inlet air temperature stablizes temperature of charge at 30~40 DEG C, opens
Opening peristaltic pump and adjusting wriggling revolution speed is 15r/min, and the quality of wall material ethyl cellulose is 80g, coating solution spray in coating solution
Stop coating, drying 10~take out after twenty minutes after complete, Microcapsules Size obtained is mainly distributed on 0.2~0.35mm, carries medicine
Rate is 33.4%.
In specific implementation, microcapsules can be divided into core material using any one group in Examples 1 to 5, any one packet
Clothing formula is wall material, and different-grain diameter, the slow-release resistance rust microcapsules of different coating weight gains are made.
Two, the Morphology analysis of slow-release resistance rust microcapsules under a scanning electron microscope:
In Fig. 1, a, b are respectively the microscopic appearance figure before 1 concrete slow-release type microcapsule of embodiment is coated and after coating, core
Material and the mass ratio of wall material are 1:0.2, it can be seen from the figure that core material particles surface is more coarse before being coated and has part clast
It falls off, is in irregular ellipsoid；Surface of microcapsule obviously becomes smooth and fine and close after coating, is in ellipsoid, partial size is also than packet
Increased before clothing.From the comparison of Fig. 1 and Fig. 2 this it appears that core material has one layer of fine and close packet in fluidized bed coating rear surface
Clothing film is formed, and the surface topography of microcapsules is also more regular, and high molecular material has carried out effective cladding to core material, resulting micro-
Capsule carrying drug ratio is high, has been up to 47.3%, significantly larger than 20% or so carrying drug ratio of the prior art.Carrying drug ratio therein
Calculating be by microcapsules sample total medicament contg and the total weight ratio of microcapsules sample obtain.In microcapsules sample
Total medicament contg be total medicament contg in the sample for determine microcapsules by the amount of colorimetric method for determining phosphate anion, pass through
The carrying drug ratio of repetition test, microcapsules can be carried out by the pharmaceutical formulation during change centrifugal granulator and fluidized bed coating
It adjusts.
In Fig. 2, a, b are respectively the slow-release resistance rust microcapsules that prepare of embodiment 2 and embodiment 3 in scanning electron microscope
Under microscopic appearance figure, it can be seen from the figure that the particle diameter distribution of microcapsules is in 0.2-0.3mm, embodiment 3 in embodiment 2
The particle diameter distribution of microcapsules is in 0.35-0.5mm, it is seen that can be to microcapsules by the technological parameter during change centrifugal granulator
Particle size be adjusted, and obtained Microcapsules Size is small.
Three, release rule analysis of the slow-release resistance rust microcapsules of different weight gains in simulated seawater concrete solution:
Slow-release resistance rust microcapsules in embodiment 1 are placed in simulated seawater concrete solution, which is pH value 12
~13 calcium hydroxide solution wherein also containing the NaCl of 3.5wt% in solution, and prepares core material using the method for embodiment 1
Mass ratio with wall material is that the resistance rust microcapsules of 1:0.1,1:0.2,1:0.3 compare, that is, increase weight 10%, 20%, 30% work
Comparison after impregnating different number of days, the amount of fluorine ion in different time solution is impregnated by ion-chromatographic determination, to calculate
Out in microcapsules sodium monofluorophosphate (MFP) rate of release.
Fig. 3 is the rate of release figure of the slow-release resistance rust microcapsules of different weight gains in embodiment 1, it can be seen from the figure that
Three kinds of microcapsules are very fast in preceding 7 days rates of release, and subsequent rate of release is gradually slack-off, after reaching 60 days, 10% weight gain it is micro-
Capsule Release of core material amount has reached 84%, and the microcapsules Release of core material amount of 20% weight gain is 56%, the microcapsules core of 30% weight gain
Material burst size is 44%, it can be seen that different wall material weight gains have larger impact to the rate of release of microcapsules core material.Wall material weight gain
Bigger, wall material is thicker, and with the increase of wall material thickness, rate of release of the microcapsules in simulated seawater concrete solution also with
Reduction, slow release effect is more obvious, and deenergized period is obviously prolonged.But wall material weight gain is blocked up, will affect resistance rust effect.From list
It is seen in the rate of release and burst size of sodium fluoro phosphate, the resistance rust microcapsules of this method preparation can touch in simulated seawater solution
Hair, and there is good slow releasing function, deenergized period is longer.
Four, the slow-release resistance rust microcapsules of different weight gains impregnate 60 days microscopic appearances in simulated seawater concrete solution
Comparison:
Slow-release resistance rust microcapsules in embodiment 1 are placed in simulated seawater concrete solution, which is pH value 12
~13 calcium hydroxide solution wherein also containing the NaCl of 3.5wt% in solution, and prepares core material using the method for embodiment 1
Mass ratio with wall material is that the resistance rust microcapsules of 1:0.1,1:0.2 and 1:0.3 compare, and after impregnating 60 days, it is micro- to take out part
Capsule sufficiently observes its microscopic appearance with scanning electron microscope after drying.
Fig. 4 is the microscopic appearance for the slow-release resistance rust microcapsules that core material and the mass ratio of wall material are 1:0.1 in embodiment 1
Figure, wall material obviously cracks after microcapsules impregnate 60 days in simulated seawater concrete solution, and core material also starts spalling after absorbing water,
Core material starts to release.
Fig. 5 is the microscopic appearance for the slow-release resistance rust microcapsules that core material and the mass ratio of wall material are 1:0.2 in embodiment 1
Figure, wall material has obvious crackle after microcapsules impregnate 60 days in simulated seawater concrete solution, but does not split completely, core material portion
Divide spalling, level of breakage is lower than the microcapsules that core material and the mass ratio of wall material are 1:0.1.
Fig. 6 is the microscopic appearance for the slow-release resistance rust microcapsules that core material and the mass ratio of wall material are 1:0.3 in embodiment 1
Figure, wall material has partial crack generation after microcapsules impregnate 60 days in simulated seawater concrete solution, but remains to envelope completely
Core material, core material only partially release, and level of breakage is lower than the microcapsules that core material and the mass ratio of wall material are 1:0.2.
Thickness continues to thicken, and the Release of core material period is longer.
The slow-release resistance rust microcapsules of above embodiments of the present invention are a kind of slow-release resistance rust applied to armored concrete
Microcapsules are based particularly on the microcapsules of triggering and energy long-term sustained release in simulated seawater concrete solution.It is different from traditional micro-
Capsule, microcapsules according to the present invention, wall material thickness can be carried out according to the requirement to rate of release and resistance rust time
Regulation achievees the purpose that control release.
There are the resistance rust microcapsules of slow release effect using the preparation of the method for centrifugal granulator and fluidized bed coating, there is preparation stream
The features such as journey is simple, utilization rate of raw materials is high, the Release of core material period is long, rate of release is controllable can overcome the inorganic resistance rust of tradition
Agent using when additive amount is big, have the shortcomings that higher toxicity, carcinogenicity, release are too fast.The slow-release resistance rust of above embodiments is micro-
Capsule can be added in armored concrete together with coarse sand and cement, can effectively reduce the damage when in use of inorganic corrosion inhibitor
It loses, improves its service efficiency.
Environment of the practical armored concrete in sea water solution more, the Er Qiehuan more complicated than simulated seawater concrete solution
Border pH value declines faster, therefore the rate of release of slow-release resistance rust microcapsules in practical applications can be slower, and discharges week
Phase is longer than in simulated seawater concrete solution.
There are the microcapsules of slow release effect using the preparation of the method for centrifugal granulator and fluidized bed coating, the size of core material can be with
By changing centrifugal basket disk rotating speed, being adjusted for night speed, blow rate required etc., the core material particles after general drying are irregular
Elliposoidal, diameter is between 0.1-0.4mm；The thickness of wall material can be carried out by changing the weight of high molecular material in coating solution
Adjustment, the surface for completing microcapsules after being coated become smooth and fine and close, are in ellipsoid, diameter is between 0.15-0.5mm.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (4)
1. a kind of preparation method of the slow-release resistance rust microcapsules applied to armored concrete comprising core material and wall material, it is special
Sign is: the core material includes inorganic corrosion inhibitor and auxiliary material, and the wall material includes the high molecular material for controlling corrosion inhibitor release；Institute
State the component and its parts by weight that core material includes are as follows: 100 parts of inorganic corrosion inhibitor, 90 ~ 110 parts of microcrystalline cellulose, hydroxypropyl methyl
2 ~ 4 parts of cellulose；The core material and the mass ratio of wall material are 1:(0.1 ~ 0.4)；The slow-release resistance rust microcapsules are elliposoidal,
The diameter of the core material is 0.1 ~ 0.4mm before being coated, and the diameter of microcapsules is 0.15-0.5mm after coating；It is described to be applied to reinforcing bar
The slow-release resistance rust microcapsules of concrete are prepared using following steps:
Step S1: centrifugal process prepares core material；
It being added in centrifugation apparatus after inorganic corrosion inhibitor and auxiliary materials and mixing, successively open air blast, blower speed is 400 ~
600r/min, rotary speed are 400 ~ 600r/min, open peristaltic pump feed flow, wriggling revolution speed is 10 ~ 20r/min, to material
Peristaltic pump is closed when being in cotton-shaped flowing in pot, continues to rotate, polish, is taken out when the size of particle and hardness reach requirement dry
It is dry, core material is made；
Step S2: coating solution is prepared；
The high molecular material of the control corrosion inhibitor release is added in organic solvent, in the heating and stirring of magnetic stirring apparatus
Under transparent uniform coating solution is made；
Step S3: fluidized bed coating；
Core material is placed in fluidized bed, under coating mode, adjust 800 ~ 1300rpm of rotation speed of fan and aspiration pressure 0.9 ~
0.12MPa, and start to preheat, adjusting inlet air temperature makes temperature of charge at 30 ~ 40 DEG C, opens peristaltic pump and starts hydrojet coating, packet
Clothing liquid stops coating and drying after having sprayed；The high molecular material of the control corrosion inhibitor release is polystyrene or polymethyl
Sour methyl esters, the organic solvent are ethyl acetate, the quality of the polystyrene or polymethyl methacrylate and ethyl acetate
Than for 1:(10 ~ 15)；Alternatively, the high molecular material of the control corrosion inhibitor release is ethyl cellulose, the ethyl cellulose
Mass ratio with ethyl acetate is 1:(12 ~ 15)；Alternatively, the high molecular material of the control corrosion inhibitor release is polycarbonate,
The mass ratio of the polycarbonate and ethyl acetate is 1:(13 ~ 16).
2. the preparation method of the slow-release resistance rust microcapsules according to claim 1 applied to armored concrete, feature
It is: the component and its parts by weight that the core material includes are as follows: 100 parts of inorganic corrosion inhibitor, 95 ~ 105 parts of microcrystalline cellulose, hydroxypropyl
2.5 ~ 3 parts of ylmethyl cellulose.
3. the preparation side described in any one applied to the slow-release resistance rust microcapsules of armored concrete according to claim 1 ~ 2
Method, it is characterised in that: the inorganic corrosion inhibitor includes calcium nitrite, sodium monofluorophosphate, cerous nitrate, calcium hydroxide and barium hydroxide
At least one of.
4. the preparation method of the slow-release resistance rust microcapsules according to claim 3 applied to armored concrete, feature
Be: in step S1, the blower speed is 400 ~ 500r/min, and rotary speed is 500 ~ 600r/min, wriggling revolution speed
For 10 ~ 15r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610814609.1A CN106431069B (en) | 2016-09-09 | 2016-09-09 | A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610814609.1A CN106431069B (en) | 2016-09-09 | 2016-09-09 | A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106431069A CN106431069A (en) | 2017-02-22 |
| CN106431069B true CN106431069B (en) | 2019-06-25 |
Family
ID=58168378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610814609.1A Active CN106431069B (en) | 2016-09-09 | 2016-09-09 | A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106431069B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673678B (en) * | 2017-11-03 | 2020-06-05 | 西安东大洋混凝土有限公司 | Recycled concrete and preparation method thereof |
| CN113387661B (en) * | 2021-07-24 | 2022-08-19 | 西安天盛混凝土有限公司 | Concrete and preparation method thereof |
| CN114920493B (en) * | 2022-06-22 | 2023-03-28 | 水利部交通运输部国家能源局南京水利科学研究院 | PH self-immune hydrotalcite rust inhibitor and preparation method and application thereof |
| CN115521107B (en) * | 2022-09-13 | 2023-09-29 | 华新水泥股份有限公司 | Reinforced concrete cured by carbon dioxide and preparation method thereof |
| CN115925310A (en) * | 2022-09-27 | 2023-04-07 | 深圳大学 | Response release rust-resisting microcapsule for waste-fixing marine concrete and preparation method thereof |
| CN115650630B (en) * | 2022-09-27 | 2024-04-16 | 深圳大学 | Compound rust-resistant microcapsule and preparation method thereof |
| CN118063173B (en) * | 2024-04-24 | 2024-07-23 | 浙江大学 | Low-shrinkage seawater concrete with chloride ion curing capability and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517587A (en) * | 2011-11-25 | 2012-06-27 | 深圳大学 | Ethyl cellulose type calcium nitrite corrosion inhibitor and preparation method thereof |
-
2016
- 2016-09-09 CN CN201610814609.1A patent/CN106431069B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517587A (en) * | 2011-11-25 | 2012-06-27 | 深圳大学 | Ethyl cellulose type calcium nitrite corrosion inhibitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106431069A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106431069B (en) | A kind of slow-release resistance rust microcapsules and preparation method thereof applied to armored concrete | |
| CN102690645B (en) | Sustained-release gel-breaking type fracturing propping agent and preparation method thereof | |
| CN108147705B (en) | Magnesium efficient anti-cracking agent for cement concrete, preparation method and application thereof | |
| EP2471846A1 (en) | Polyacrylic acid (salt) water absorbent resin and method for producing same | |
| CN108440704B (en) | Boiling water resistant high-adhesion double-component acrylate emulsion and preparation method thereof | |
| CN107446092A (en) | A kind of acrylic acid epoxy core-shell emulsion and preparation method thereof | |
| CN106916260A (en) | A kind of preparation method of hud typed porous high water absorption microballoon | |
| US20240254057A1 (en) | High-strength self-healing capsule and production process thereof | |
| CN105366980B (en) | A kind of method that spray drying prepares polymer wrapped resistance rust thing microcapsules | |
| CN113430439B (en) | Phase distribution uniformity control method of high-toughness active tungsten alloy | |
| CN105731901B (en) | A kind of production technology of the water-fast fire-resistive construction material of high strength loop environment friendly flame-retardant | |
| CN102070730B (en) | A kind of method of preparing emulsion with multivariate particle size distribution in situ | |
| Zuo et al. | Preparation and behavior of sustained-release corrosion inhibitor microcapsules by centrifugation-coating method | |
| CN117263501A (en) | Preparation method and application of yttrium-containing hollow glass spheres | |
| KR102021926B1 (en) | Coated granular fertilizer preventing solidification and floating in water and manufacturing method thereof | |
| CN112299745A (en) | Slow-release concrete curing agent and preparation method and application thereof | |
| CN115418203B (en) | Fiber polymer plugging agent for drilling fluid and preparation method thereof | |
| CN104177556B (en) | Plastic stabilizer and preparation method thereof | |
| CN113248235B (en) | Preparation method of solid spherical AT13 spraying feed with low process cost | |
| CN107445627B (en) | A kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder | |
| CN105330191A (en) | Preparation method of concrete internal curing agent | |
| CN104906060A (en) | Indapamide slow-release hypertension pill and preparation method thereof | |
| CN101954086A (en) | Waterborne enteric coating powder as well as preparation and using methods thereof | |
| CN112194938A (en) | External wall interface agent and preparation method thereof | |
| CN103143025A (en) | Water-soluble enteric coating powder as well as preparation method and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |