CN108822579A - A kind of modification shell powder preparation method with good dispersion - Google Patents
A kind of modification shell powder preparation method with good dispersion Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Abstract
The present invention provides a kind of modification shell powder preparation method with good dispersion, including step in detail below:(1) shell after cleaning up is mechanically pulverized, suitable quantity of water is added, class mortar substance is made, and is filtered by 400 mesh filter screens, it is then dry under middle low temperature, shell powder is made;(2) add water to be configured to sea shell micropowder slurry at normal temperature shell powder, under electric mixer low speed dispersion condition, phosphoric acid,diluted is added, reacts it sufficiently, after reaction, through filtering, drying, break up up to inorganic acid modification biological calcium carbonate;(3) slurry that mass fraction is 5% will be made, organic modifiers are then added under agitation after the tentatively modified conch meal body hypothermia of phosphoric acid corrosion is dry.The technical problem to be solved in the present invention is to provide a kind of calcium carbonate that not only can have quantitatively removed as desired in shell powder, but also the shell powder preparation method of good dispersibility and stability can be kept in organic system.
Description
Technical field
The present invention relates to a kind of shell powder, preparation method thereof, especially a kind of modification conch meal system with good dispersion
Preparation Method.
Background technique
China's shellfish yield of about 12,000,000 tons/year, account for Gross World Product close to 60%, but for a long time China for
The utilization overwhelming majority of shellfish is confined to edible part, and the shell part for accounting for 60% or more shellfish quality but seldom processes benefit
With, produce a large amount of waste shells, be not used effectively not only, but also be largely deposited in as solid waste seabeach or its
His soot, waste of resource pollute environment.It is this based on calcium carbonate and containing a small amount of organic matter how shell is efficiently used
Biological material is people's hot spot of interest all the time.Although conch meal is used as animal feeding-stuff additive and calcium supplement already
It uses, but its actual amount is relatively fewer, can not effectively consume a large amount of shellfish deposits generated every year.In recent years, by shell
Powder causes people's broad interest for Material Field.In the related art, shell powder is had become applied to anticorrosive paint
For current important industry.
In order to prepare High Performance Corrosion Protective Coatings, related personnel using be added in anticorrosive paint system suitable pigments and fillers,
The modes such as auxiliary agent improve the performance of coating, and wherein to be that current anticorrosive paint field is the most commonly used fill out for calcium carbonate and glass flake
Material, but inorganic carbonate calcium powder body and glass flake all have significant hydrophilic and oleophobic characteristic and highly polar, cause it viscous with resin
Bad, poor compatibility is tied, disperses unevenly, to sprawl difficulty in organic media, so that defect is generated inside film, reduction property
Energy.Shell pearl layer is the canonical biometric mineral material being made of calcium carbonate and large biological molecule compared with above-mentioned material, is one
Kind natural inorganic-organic composite material, while shell itself has typical lamellar structure, by clam shell feature, it is inorganic-
Organic phase regulates and controls and is modified, and development and application are in the bioactivity carbonic acid calcium of coating, and added value is high, and demand is big, and application prospect is wide
It is wealthy, compared with traditional inorganic carbonate calcium and glass flake filler, there is direct application prospect in corrosion and protection field.Cause
This waste shell for generating the related industries such as aquaculture passes through modification application Yu Haiyang anticorrosive paint industry and domestic and international institute
The Green Development of promotion, the thinking of development of low-carbon cycle bring out the best in each other.Suitable method regulation and control shell is taken among these
The ingredient of source calcium carbonate powder and the activity of organic group just become the important research direction in this field.
State Intellectual Property Office discloses a kind of conch meal method of modifying (CN201710183429.2), specifically by height
The method of temperature calcining and grinding prepares a kind of shell powder that diameter is about 10um.This method passes through high-temperature calcination twice, highest
Calcination temperature reaches 1200 DEG C, and the contained organic active group of shell itself substantially completely disappears at this high temperature, obtains
To product be almost pure inorganic phase calcium carbonate powder, lose this natural inorganic-organic composite material characteristic of shell,
It is unfavorable for subsequent dispersion and application in the systems such as coating, resin.
State Intellectual Property Office discloses a kind of shell raw powder's production technology (CN201610697737.2), specially logical
It crosses soaking and washing and carries out drying drying in high temperature (about 450-550 DEG C), and ground.This method uses simple physics
It crushes and medium temperature calcination method prepares shell powder, it, can not be accurate although remaining the active organic group on surface
Inorganic, organic principle the ratio in powder is controlled, while being further modified without carrying out surface, powder is in organisms such as coating
Dispersibility and stability in system still need to be further increased.
State Intellectual Property Office discloses a kind of preparation method (CN201710499629.9) of conch meal modified calcium carbonate,
Specially:Shell is crushed and is ground to partial size 3mm hereinafter, subsequent high-temperature roasting, is added suitable dispersing agent and water, grinding,
Filtering, is codissolved in water, high-speed stirred with micron-sized calcium carbonate powder, filters, dry.The purpose of this method is by by shellfish
Shell powder is adsorbed on small calcium carbonate powder surface, has the function that its good antibacterial and absorption pollutant, but this method
Obtained modification shell powder process is complicated, at high cost, and high-temperature calcination destroys the organic active group of shell powder, unfavorable
In the dispersion in the oleaginous systems such as coating, resin.
State Intellectual Property Office discloses a kind of sea shell micropowder filler preparation method (CN02125731.0), specially:It will
Shell is crushed after being cleaned, and then so that the macromolecular chain in shell is degraded by ultraviolet light and ultrasonication, to make
Shell powder further refines.It is disadvantageous in that the organic group not made full use of in shell, it is also further without carrying out
Surface it is modified, affect dispersion effect and stability of the powder of manufacture in organic system.
State Intellectual Property Office disclose it is a kind of go in water removal natural adsorbent and preparation method thereof of heavy metal ion and
It is then crushed by drying the shell cleaned up using (CN200910070793.3), finally it is carried out with ball mill
It crushes, grinding, obtains conch meal adsorbent.But this patent is imitated only with the absorption of shell powder counterweight metal ion
Fruit is not modified shell powder.
State Intellectual Property Office discloses a kind of conch meal and preparation method thereof and method of modifying and purposes
(CN201510481985.9), it after specially cleaning shell, is calcined by three-stage, conch meal is made in grinding, and is answered
For in antibacterial, taste removal coating.But this method underuses organic group in shell, also without carrying out further surface
It is modified, affect dispersion effect and stability of the powder of manufacture in organic system.
State Intellectual Property Office discloses the preparation method and product of a kind of sour modified superfine conch meal
(CN201310025460.5), the patent is by the way that certain density acid solution to be added in sea shell micropowder slurry, and ground, dry
Dry obtained fineness 0.01-5um tide conch meal, but the patent to shell powder carry out coupling agent modification, it is unfavorable
In dispersion of the modified powder in organic system.
State Intellectual Property Office discloses a kind of method of shell hydro-thermal process preparation high-purity calcite calcium carbonate micropowder
(CN201310037909.X), this method is conducive to shell by the hydro-thermal process preparation calcite calcium carbonate in autoclave
It recycles, but the patent does not carry out the modification of coupling agent to shell powder, is unfavorable for modified powder in organic system
Dispersion.
State Intellectual Property Office discloses a kind of preparation method (CN201510938663.2) of modified conch meal, specially
Using carbon nanotube and calcium carbonate powder doping vario-property, a kind of composite material of high heavy metal ion adsorbed property, but the party are prepared
Method does not inquire into the function and effect and dispersion effect of organic group in the calcium carbonate powder of shell source.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carbon that both can have quantitatively removed as desired in shell powder
Sour calcium, the modified calcium carbonate powder made retain calcium carbonate and organic active ingredients in required ratio;It again can be by organic
Modifying agent increases the activity of powder, is maintained at the shell powder preparation method of good dispersibility and stability in organic system.
In order to solve the above technical problems, the present invention provides a kind of modification conch meal body preparation side with good dispersion
Method, including step in detail below:
(1) shell after cleaning up is mechanically pulverized, suitable quantity of water is added, class mortar substance is made, and passes through
The filtering of 400 mesh filter screens, it is then dry under middle low temperature, shell powder is made;
(2) water is added to be configured to sea shell micropowder slurry at normal temperature the shell powder, in electric mixer low speed point
Dissipate under the conditions of, be slowly added to phosphoric acid,diluted into sea shell micropowder slurry while stirring in proportion, after being added dropwise, continue stirring 30~
It 60 minutes, reacts it sufficiently, after reaction, through filtering, drying, breaks up up to inorganic acid modification biological calcium carbonate;
(3) slurry that mass fraction is 5% will be made after the tentatively modified conch meal body hypothermia of phosphoric acid corrosion is dry
Material, is then added organic modifiers under agitation, and the organic modifiers are calcium stearate, stearic acid, γ-aminopropyl
Triethoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, three oleic acid acyloxy titanate esters of isopropyl, chelating
One of type titanate coupling agent, aluminate coupling agent, low temperature drying.
Preferably, as further Optimal improvements, the organic modifiers in step (2) are calcium stearate, hard
Resin acid, gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, three oleic acid acyl-oxygen of isopropyl
Base titanate esters, chelating titanate coupling agent, two kinds in mass ratio 1 in aluminate coupling agent:1 mixing composition, additive amount
The respectively 0.1%-10% of inorganic acid modification biological Paris white weight.
Preferably, as further Optimal improvements, the conch meal obtained by 400 mesh filter screens of the step (1)
Body partial size is about 10-50um, and the middle low temperature is 60-100 DEG C.
Preferably, as further Optimal improvements, the mass content of sea shell micropowder slurry is 5 in the step (2)
~30%, the quality of the phosphoric acid being added dropwise is the 5~30% of sea shell micropowder quality, the mass concentration of dilute phosphoric acid solution is 5~
40%.
Preferably, as further Optimal improvements, the low temperature in the step (3) is less than or equal to 60 DEG C.
Compared with prior art, it is an advantage of the invention that:The activated Calcium carbonate powder of this method preparation is determined to more
Typical sheet, material analysis test prove that the retention of its surface has a certain amount of organic group, effect are dispersed in oleaginous system
Fruit is good, not easy to reunite, can be applied to anticorrosive paint system, while efficiently using waste shell, turns waste into wealth, and realizes resource
Recycle, be conducive to sustainable development.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the influence schematic diagram after different modifying agent of the invention add to powder oil absorption.
Fig. 2 is the influence schematic diagram of different modifier modifications of the invention to the settling volume of 10p-zyb powder.
Fig. 3 is the material phase analysis schematic diagram of shell powder rear before modified of the invention.
Fig. 4 is the infrared spectroscopy schematic diagram one of shell powder rear before modified of the invention.
Fig. 5 is the infrared spectroscopy schematic diagram two of shell powder rear before modified of the invention.
Fig. 6 is the infrared spectroscopy schematic diagram three of shell powder rear before modified of the invention.
Fig. 7 is the SEM schematic diagram 1 of modification shell powder of the invention.
Fig. 8 is the SEM schematic diagram 2 of modification shell powder of the invention.
Specific embodiment
To enable the above objects, features and advantages of the present invention to be clearer and more comprehensible, modification shell system of the invention hereafter
Preparation Method will be cooperated appended relevant drawings, be elaborated with preferred embodiment.
The modification shell powder preparation method of the present embodiment, including step in detail below:
(1) shell after cleaning up is mechanically pulverized, suitable quantity of water is added, class mortar substance is made, and passes through
The filtering of 400 mesh filter screens, it is then dry under middle low temperature, shell powder is made;
(2) water is added to be configured to sea shell micropowder slurry at normal temperature the shell powder, in electric mixer low speed point
Dissipate under the conditions of, be slowly added to phosphoric acid,diluted into sea shell micropowder slurry while stirring in proportion, after being added dropwise, continue stirring 30~
It 60 minutes, reacts it sufficiently, after reaction, through filtering, drying, breaks up up to inorganic acid modification biological calcium carbonate;
(3) slurry that mass fraction is 5% will be made after the tentatively modified conch meal body hypothermia of phosphoric acid corrosion is dry
Material, is then added organic modifiers under agitation, and the organic modifiers are calcium stearate, stearic acid, γ-aminopropyl
Triethoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, three oleic acid acyloxy titanate esters of isopropyl, chelating
One of type titanate coupling agent, aluminate coupling agent, low temperature drying.Organic modifiers in step (2) can also be hard
Resin acid calcium, stearic acid, gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, isopropyl
Three oleic acid acyloxy titanate esters, chelating titanate coupling agent, two kinds in mass ratio 1 in aluminate coupling agent:1 mixing group
At additive amount is respectively the 0.1%-10% of Paris white weight.It is obtained by 400 mesh filter screens of the step (1)
Shell diameter of particle be about 10-50um, the middle low temperature be 60-100 DEG C.The quality of sea shell micropowder slurry in step (2)
Content is 5~30%, and the quality for the phosphoric acid being added dropwise is the 5~30% of sea shell micropowder quality, the mass concentration of dilute phosphoric acid solution
It is 5~40%.Low temperature in step (3) is less than or equal to 60 DEG C.
As shown in Figures 1 to 8, lower heat drying temperature can be effectively retained organic group in shell powder, protect
Demonstrate,prove the activity of powder;The reacting dose of inorganic phase in conch meal body can be quantitatively controlled by control inorganic acid dosage;Pass through acid etching
It can be applied to the high activity Paris white of the oleaginous systems such as coating with the modified preparation of inorganic-organic hybrid of the methods of graft
Body.
Fig. 1 shows the influence after the addition of different modifying agent to powder oil absorption;Fig. 2 shows different modifier modifications to 10p-
The influence of the settling volume of zyb powder;The material phase analysis of shell powder after Fig. 3 is shown before modified, before modified after primary chemical
Ingredient is all the mixture of calcite and aragonite, still remains the basis of calcium carbonate powder;Fig. 4 to fig. 6 is before modified
The infrared spectroscopy of shell powder afterwards, it can be seen from the figure that all remaining the 1500cm of carbonate mineral after before modified-1With
876cm-1Characteristic peak;Comparison diagram 4 and Fig. 5 discovery are in 3000cm-1~2000cm-1There is certain platform, shows phosphoric acid
The structure for changing shell powder is added, realizes certain modified effect;And be added it is coupling agent modified after in 2920cm-1With
2840cm-1There is the absorption peak of methyl and methylene, illustrate it is coupling agent modified after be firmly bonded to shell powder surface, rise
Modified effect is arrived.Fig. 7 and Fig. 8 is modified shell powder SEM microscopic appearance figure, and as can be seen from the figure modified powder contains piece
Shape and prism-shaped particle, sheet-like particle partial size are about 10 μm, some are fuzzy for powder surface, corner angle fuzzy, are phosphoric acid,diluted corrosion
The part calcium carbonate for having fallen shell pearl layer surface allows surface to become coarse, at the same it is coupling agent modified after be coated on powder surface
Caused, this is conducive to powder dispersion effect and stability in the oleaginous systems such as coating, resin.
In conclusion in the present invention associated materials and the relevant technologies utilization, enable the preparation method have lot of advantages,
As both can quantitatively removed the calcium carbonate in shell powder as desired, the modified calcium carbonate powder made is protected in required ratio
Stay calcium carbonate and organic active ingredients;The activity that powder can be increased by organic modifiers again, is maintained at good in organic system
Good dispersibility and stability.Therefore, the present invention has substantive distinguishing features outstanding and significant progress.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of modification shell powder preparation method with good dispersion, it is characterised in that:Including step in detail below:
(1) shell after cleaning up is mechanically pulverized, suitable quantity of water is added, class mortar substance is made, and passes through 400 mesh
Strainer filtering, it is then dry under middle low temperature, shell powder is made;
(2) add water to be configured to sea shell micropowder slurry at normal temperature the shell powder, disperse item in electric mixer low speed
Under part, it is slowly added to phosphoric acid,diluted into sea shell micropowder slurry while stirring in proportion, after being added dropwise, continues 30~60 points of stirring
Clock reacts it sufficiently, after reaction, through filtering, drying, breaks up up to inorganic acid modification biological calcium carbonate;
(3) slurry that mass fraction is 5% will be made after the tentatively modified conch meal body hypothermia of phosphoric acid corrosion is dry, with
Organic modifiers are added under agitation afterwards, the organic modifiers are calcium stearate, stearic acid, three second of γ-aminopropyl
Oxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, three oleic acid acyloxy titanate esters of isopropyl, chelating type titanium
One or both of acid esters coupling agent, aluminate coupling agent, low temperature drying.
2. the modification shell powder preparation method according to claim 1 with good dispersion, it is characterised in that:Step
(2) organic modifiers in are calcium stearate, stearic acid, gamma-aminopropyl-triethoxy-silane, γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane, three oleic acid acyloxy titanate esters of isopropyl, chelating titanate coupling agent, aluminate coupling agent
In two kinds in mass ratio 1:1 mixing composition, additive amount is respectively the 0.1%- of inorganic acid modification biological calcium carbonate quality
10%.
3. the modification shell powder preparation method according to claim 1 or 2 with good dispersion, it is characterised in that:
It is about 10-50um by the shell diameter of particle that 400 mesh filter screens of the step (1) obtain, the middle low temperature is 60-
100℃。
4. the modification shell powder preparation method according to claim 3 with good dispersion, it is characterised in that:It is described
The step of (2) in the mass content of sea shell micropowder slurry be 5~30%, the quality of the phosphoric acid being added dropwise is sea shell micropowder quality
5~30%, the mass concentration of dilute phosphoric acid solution is 5~40%.
5. the modification shell powder preparation method according to claim 4 with good dispersion, it is characterised in that:It is described
The step of (3) in low temperature be less than or equal to 60 DEG C.
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Cited By (7)
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CN112341841A (en) * | 2020-10-15 | 2021-02-09 | 四川轻化工大学 | Preparation method and application of long-acting natural multifunctional additive |
CN112480715A (en) * | 2020-12-08 | 2021-03-12 | 深圳市锦昊辉实业发展有限公司 | Modified heavy calcium carbonate and preparation method and application thereof |
CN112574598A (en) * | 2021-01-25 | 2021-03-30 | 广西华纳新材料科技有限公司 | Method for increasing specific surface area of heavy calcium carbonate |
CN113881249A (en) * | 2021-11-24 | 2022-01-04 | 吴振清 | Oyster shell powder composite filler with super-hydrophobicity and preparation method thereof |
CN113930860A (en) * | 2021-09-22 | 2022-01-14 | 暖博士新材料(无锡)有限公司 | Shellfish nanofiber |
CN114292676A (en) * | 2021-11-30 | 2022-04-08 | 中润油新能源股份有限公司 | Pollution-free methanol-based clean fuel and preparation method thereof |
CN116396649A (en) * | 2023-05-26 | 2023-07-07 | 河北宇阳泽丽防水材料有限公司 | Reflective heat-insulating waterproof coating |
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CN103571235A (en) * | 2013-10-28 | 2014-02-12 | 浙江大学舟山海洋研究中心 | Preparation method of prismatic biological calcium carbonate |
CN106084891A (en) * | 2016-06-06 | 2016-11-09 | 广东贝尤安新材料科技有限公司 | A kind of modified conch meal calcine technology |
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CN103571235A (en) * | 2013-10-28 | 2014-02-12 | 浙江大学舟山海洋研究中心 | Preparation method of prismatic biological calcium carbonate |
CN106084891A (en) * | 2016-06-06 | 2016-11-09 | 广东贝尤安新材料科技有限公司 | A kind of modified conch meal calcine technology |
CN106883642A (en) * | 2017-03-24 | 2017-06-23 | 南通苏东新型外墙保温板有限公司 | A kind of method of modifying of oyster shell whiting |
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CN112341841A (en) * | 2020-10-15 | 2021-02-09 | 四川轻化工大学 | Preparation method and application of long-acting natural multifunctional additive |
CN112480715A (en) * | 2020-12-08 | 2021-03-12 | 深圳市锦昊辉实业发展有限公司 | Modified heavy calcium carbonate and preparation method and application thereof |
CN112574598A (en) * | 2021-01-25 | 2021-03-30 | 广西华纳新材料科技有限公司 | Method for increasing specific surface area of heavy calcium carbonate |
CN113930860A (en) * | 2021-09-22 | 2022-01-14 | 暖博士新材料(无锡)有限公司 | Shellfish nanofiber |
CN113930860B (en) * | 2021-09-22 | 2023-09-01 | 暖博士新材料(无锡)有限公司 | shellfish nanofiber |
CN113881249A (en) * | 2021-11-24 | 2022-01-04 | 吴振清 | Oyster shell powder composite filler with super-hydrophobicity and preparation method thereof |
CN114292676A (en) * | 2021-11-30 | 2022-04-08 | 中润油新能源股份有限公司 | Pollution-free methanol-based clean fuel and preparation method thereof |
CN116396649A (en) * | 2023-05-26 | 2023-07-07 | 河北宇阳泽丽防水材料有限公司 | Reflective heat-insulating waterproof coating |
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