CN101637434B - Preparation method of nuclear shell type CaCO3/SiO2 toothpaste abrasive - Google Patents
Preparation method of nuclear shell type CaCO3/SiO2 toothpaste abrasive Download PDFInfo
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- CN101637434B CN101637434B CN200910070251A CN200910070251A CN101637434B CN 101637434 B CN101637434 B CN 101637434B CN 200910070251 A CN200910070251 A CN 200910070251A CN 200910070251 A CN200910070251 A CN 200910070251A CN 101637434 B CN101637434 B CN 101637434B
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Abstract
The invention discloses a preparation method of nuclear shell type CaCO3/SiO2 toothpaste abrasive, comprising the following steps of: preparing spherical calcium carbonate grain with grain diameter being 3-15um; taking the spherical calcium carbonate grain as template and ethyl orthosilicate as silicon source; under the catalyticaction of ammonia, coating silicon dioxide on the surface of the spherical calcium carbonate grain in a collosol-gelatin way; and finally obtaining monodispersed and nuclear shell type CaCO3/SiO2 composite structure grain. The preparation method mainly comprises the step of preparing the spherical calcium carbonate grain and the step of preparing the CaCO3/SiO2 toothpaste abrasive. When the nuclear shell type CaCO3/SiO2 spherical grain is used as the toothpaste abrasive, the method has the advantages of good compatibility with fluoride, decontamination effect and friction effect as the market SiO2 abrasive toothpaste.
Description
Technical field
The present invention relates to a kind of method for preparing of nucleocapsid structure toothpaste abrasive.
Background technology
Abrasive is content is maximum in the toothpaste composition, mainly plays cleaning teeth but the effect of the tooth that do not wear and tear.Be limited to multiple factor, most at present toothpaste all are to process with the abrasive of single component, like calcium carbonate, silicon dioxide, aluminium hydroxide, calcium hydrogen phosphate, calcium pyrophosphate etc.China is widely used precipitated calcium carbonate as toothpaste abrasive; In the extensive employing of countries such as US and European is silicon dioxide or calcium hydrogen phosphate abrasive
[1](be mainly reflected in cleaning capacity, cost, with the compatibility of fluoride, to the wear intensity of tooth etc.) deficiency because the combination property of single abrasive begins to utilize methods such as mixer mill liniment or abrasive be composite to prepare toothpaste in recent years.Mix by 42% calcite in powder (calcium carbonate) and 5% precipitated hydrated silica like the employed abrasive of certain efficient desensitizing toothpaste
[2]The friction value of this toothpaste has reduced by 40%, has reduced the wearing and tearing to tooth; But the problem of the calcium carbonate and the sodium fluoride compatibility still exists in this toothpaste.And for example utilize dicalcium phosphate dehydrate and 6%SiO
2Composite and the toothpaste processed
[3]Though its wearing and tearing to tooth are very little, there are phenomenons such as jaundice is rotten in toothpaste.
Another developing direction of toothpaste abrasive is cheap calcium carbonate abrasive to be carried out the regulation and control and the modification on form and surface, thereby improves the acid resistance of calcium carbonate abrasive in toothpaste and with the compatibility of fluoride and reduce its wearing and tearing to facing.Aspect form, be reactant with sodium carbonate and calcium chloride, utilize the regulating and controlling effect of polystyrene-acrylic acid and kayexalate to synthesize the spherical calcium carbonate particle that particle diameter is 2～8 μ m respectively, but the spherical calcium carbonate particle is not carried out finishing
[4-5]Aspect finishing, can lyophobic dusts such as sodium stearate be coated in the surface of calcium carbonate particle, with the compatibility of fluoride in improvement and the toothpaste; But this method is still undesirable to the solution of calcium carbonate and fluoride compatibility problem
[6]Silicate is joined in the calcium carbonate aaerosol solution, prepare the granule of forming by silica shell and calcium carbonate core
[7], but this method preparation temperature is higher, shell is thinner, and not high with the compatibility of fluoride yet.Someone proposes to utilize 2% or 4% silicate solutions and feeds CO
2Gas carries out surface treatment to calcium carbonate, can improve calcium carbonate particle acid resistance and with the compatibility of fluoride
[8]
Along with the development of sol-gel technique, the nucleocapsid structure material had obtained development rapidly because of the controllability of nuclear, shell size and composition in recent years.As nano-calcium carbonate being joined concentration is to carry out ultra-sonic dispersion in 5%～70% the sodium silicate aqueous solution, generates colloidal sol through the reaction of silicate generation hydrolysis-condensation, thereby is deposited on the nano-calcium carbonate surface, form the nanometer CaCO with nucleocapsid structure
3/ SiO
2Compound particle
[9]In calcium carbonate suspension, add silicate in addition, feed simultaneously and contain CO
2Kiln gas carry out carbonization, the Ludox that silicate cement parses is coated on the nano-calcium carbonate surface, thereby forms hud typed silicon dioxide coated nano calcium carbonate particle
[10]But the nano-calcium carbonate in above-mentioned two methods also need add coupling agent or lipophile derivant and organic activator etc. could improve its dispersibility because agglomeration traits is serious in preparation, so that be used for fields such as coating, rubber and plastics as functional filler.If can utilize coated with silica micron-size spherical calcium carbonate granule, directly prepare monodispersed, CaCO
3/ SiO
2It then is present ideal solution that nuclear-shell composite structure particle is used for toothpaste abrasive.
Summary of the invention
The purpose of this invention is to provide the toothpaste abrasive method for preparing that a kind of core-shell silica coats the micron-size spherical calcium carbonate granule; Thereby overcome poor, the serious defective of calcium carbonate abrasive and fluoride compatibility, to reach the purpose of the higher silicon dioxide abrasive of in toothpaste is made alternative cost to tooth wear.
Technical scheme of the present invention is explained as follows: at first be to prepare the spherical calcium carbonate particle that particle diameter is 3～15 μ m; Be that template, ethyl orthosilicate (TEOS) are the silicon source with the spherical calcium carbonate particle then; Under the catalytic action of ammonia through sol-gel process with coated with silica at the spherical calcium carbonate particle surface, finally obtain monodispersed, hud typed CaCO
3/ SiO
2The composite construction particle.
Core-shell silica coats the toothpaste abrasive preparation of micron-size spherical calcium carbonate granule; With kayexalate, sodium carbonate, calcium chloride, dehydrated alcohol, cetyl trimethyl ammonium bromide, ethyl orthosilicate and ammonia is raw material, and concrete method for preparing and step are following:
Step 1: the preparation of spherical calcium carbonate particle
(1) kayexalate (be abbreviated as PSSS, molecular weight is 200000) is dissolved in the distilled water, being mixed with concentration is the PSSS solution of 0.5～15g/L.
(2) under speed is 200～1000 rev/mins stirring, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 20～50ml concentration, and the pH value that adds the ammonia regulator solution is 9.0～10.
(3) under speed was 200～1000 rev/mins stirring, adding concentration again was calcium chloride solution 20～50ml of 0.5mol/L; Continue agitating solution 1～15min, at room temperature leave standstill 24～48h then and form the spherical calcium carbonate particle, take out precipitate, filtration,, dry 1～2h for 90～100 ℃ with distilled water wash 3～5 times.
In alkaline environment, calcium chloride will generate calcium carbonate with sodium carbonate reaction, and then calcium carbonate obtains under the adjusting of PSSS solution, and dispersibility height, circularity are good, granularity is the spherical calcium carbonate particle of 3～15 μ m, are ready for use on step 2.
Step 2: hud typed CaCO
3/ SiO
2The preparation of toothpaste abrasive
(1) takes by weighing spherical calcium carbonate particle 2～10g that step 1 prepares; Join in the dehydrated alcohol of 20～150ml; And to add concentration simultaneously be cetyl trimethyl ammonium bromide aqueous solution 5～30ml of 5%; Ultra-sonic dispersion 30～60min forms suspension, and in 50～70 ℃ water bath with thermostatic control, is incubated 1～10min.
(2) under the stirring of 200～1000 rev/mins of speed, in 1～2h, slowly drip the ethyl orthosilicate of 4～30ml, the pH that adds the ammonia regulator solution simultaneously is 9.0～10.
(3) continue stirring reaction 3～6h after, the reactant deposition is taken out, to neutral, the reuse dehydrated alcohol cleans, and dries 1～2h for 90～100 ℃ with distilled water wash 3～5 times, can get granularity is 5～20 μ m, SiO
2Shell thickness is the hud typed CaCO of 0.5～1.0 μ m
3/ SiO
2The spheroidal particle of toothpaste abrasive.
Under alkali condition, cetyl trimethyl ammonium bromide is adsorbed on and forms organic/inorganic compounding template on the calcium carbonate, and hydrolysis, polycondensation take place ethyl orthosilicate above that, thereby with SiO
2Shell is coated on the calcium carbonate surface.
Raw materials such as kayexalate, sodium carbonate, calcium chloride, dehydrated alcohol, cetyl trimethyl ammonium bromide, ethyl orthosilicate and ammonia used in the above-mentioned technology of preparing scheme are analytical pure; The stirring of solution utilizes motor stirrer to realize.
Beneficial effect of the present invention is: hud typed CaCO
3/ SiO
2Spheroidal particle has when using as toothpaste abrasive that the compatibility with fluoride is good, clean effect and friction, capability and commercially available SiO
2The advantage that abrasive toothpaste is suitable.Concrete experimental data is following:
(1) with the compatibility of fluoride CaCO with same quality
3Abrasive, SiO
2Abrasive and hud typed CaCO
3/ SiO
2Particle is put into certain density Fluorinse and was soaked 7 days under 37 ℃ condition.Utilize the residual concentration of fluorion in the sulfate by ion chromatography solution afterwards, and with the compatibility of (unreacted fluorinion concentration/original fluorinion concentration) * 100% expression with fluoride.This numerical value is big more, and expression is good more with the compatibility of fluoride.CaCO
3, SiO
2With hud typed CaCO
3/ SiO
2The compatibility of particle and fluoride is followed successively by 22%, 99.5% and 93%.Hud typed CaCO is described
3/ SiO
2Particle and fluoride have the good compatibility.
(2) the hud typed CaCO of dirt-removing power utilization invention
3/ SiO
2Particle is that abrasive is mixed with toothpaste, and with commercially available SiO
2Abrasive toothpaste has carried out the dirt-removing power detection to painted eggshell together.The result shows that both dirt-removing powers are suitable.
(3) wearing and tearing ability uses friction wear testing machine and surfagauge to hud typed CaCO
3/ SiO
2Particle is self-control toothpaste, and the commercially available SiO of abrasive
2Abrasive toothpaste and CaCO
3The friction and wear behavior of abrasive toothpaste and aluminium flake is measured.The result shows, hud typed CaCO
3/ SiO
2Self-control toothpaste is slightly larger than commercially available SiO to the wear extent of aluminium flake
2Abrasive toothpaste but be merely CaCO
3Half of abrasive toothpaste.Promptly use hud typed CaCO
3/ SiO
2Toothpaste can not cause serious wearing and tearing to tooth.
Description of drawings
Fig. 1 is the grading curve of PSSS concentration spherical calcium carbonate particle when being 2g/L.
Fig. 2 is the grading curve of PSSS concentration spherical calcium carbonate particle when being 8g/L.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is done further explanation, but the invention is not restricted to these concrete embodiment.
Embodiment 1
Take by weighing 1g PSSS and be dissolved in the 1000ml distilled water, being mixed with concentration is the PSSS solution of 1g/L.Under 300 rev/mins mixing speed, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 40ml concentration, and the pH value that adds the ammonia regulator solution is 10.Then under 300 rev/mins mixing speed, adding concentration once more is the calcium chloride solution 40ml of 0.5mol/L; Continue agitating solution 10min, at room temperature leave standstill 48h then.Take out precipitate, filtration, with distilled water 3～5 times, 90～100 ℃ can obtain the spherical calcium carbonate particle that mean diameter is 13.5 μ m after drying 1～2h.
Take by weighing above-mentioned spherical calcium carbonate particle 6g, join in the dehydrated alcohol of 80ml, and to add concentration simultaneously be 5% cetyl trimethyl ammonium bromide aqueous solution 20ml that ultra-sonic dispersion 45min forms suspension, and in 70 ℃ water bath with thermostatic control, is incubated 5min.Then under 300 rev/mins mixing speed, in 2h, slowly drip the ethyl orthosilicate of 20ml, the pH that adds the ammonia regulator solution simultaneously is 10.After continuing stirring reaction 5h, the reactant deposition is taken out; And with distilled water 3～5 times to neutral, the reuse dehydrated alcohol cleans, can obtain mean diameter behind 90～100 ℃ of oven dry 1～2h is 15 μ m, SiO
2Shell thickness is 0.5～1.0 μ m, hud typed CaCO
3/ SiO
2The toothpaste abrasive spheroidal particle.
Take by weighing 2g PSSS and be dissolved in the 1000ml distilled water, being mixed with concentration is the PSSS solution of 2g/L.Under 500 rev/mins mixing speed, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 25ml concentration, and the pH value that adds the ammonia regulator solution is 10.Then under 500 rev/mins mixing speed, adding concentration once more is the calcium chloride solution 25ml of 0.5mol/L; Continue agitating solution 10min, at room temperature leave standstill 24h then.Take out precipitate, filtration, with distilled water 3～5 times, 90～100 ℃ can obtain the spherical calcium carbonate particle (Fig. 1) that mean diameter is 11.2 μ m after drying 1～2h.
Take by weighing above-mentioned spherical calcium carbonate particle 2g, join in the dehydrated alcohol of 30ml, and to add concentration simultaneously be 5% cetyl trimethyl ammonium bromide aqueous solution 10ml that ultra-sonic dispersion 30min forms suspension, and in 50 ℃ water bath with thermostatic control, is incubated 5min.Follow under 500 rev/mins mixing speed, the ethyl orthosilicate of slow Dropwise 5 ml in 2h, the pH that adds the ammonia regulator solution simultaneously is 10.After continuing stirring reaction 3h, the reactant deposition is taken out; And with distilled water 3～5 times to neutral, the reuse dehydrated alcohol cleans, can obtain mean diameter behind 90～100 ℃ of oven dry 1～2h is 12 μ m, SiO
2Shell thickness is 0.5～0.8 μ m, hud typed CaCO
3/ SiO
2The toothpaste abrasive spheroidal particle.
Embodiment 3
Take by weighing 4g PSSS and be dissolved in the 1000ml distilled water, being mixed with concentration is the PSSS solution of 4g/L.Under 200 rev/mins mixing speed, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 30ml concentration, and the pH value that adds the ammonia regulator solution is 10.Then under 200 rev/mins mixing speed, adding concentration once more is the calcium chloride solution 30ml of 0.5mol/L; Continue agitating solution 10min, at room temperature leave standstill 24h then.Take out precipitate, filtration, with distilled water 3～5 times, 90～100 ℃ can obtain the spherical calcium carbonate particle that mean diameter is 5.5 μ m after drying 1～2h.
Take by weighing above-mentioned spherical calcium carbonate particle 2g, join in the dehydrated alcohol of 30ml, and to add concentration simultaneously be 5% cetyl trimethyl ammonium bromide aqueous solution 10ml that ultra-sonic dispersion 30min forms suspension, and in 60 ℃ water bath with thermostatic control, is incubated 5min.Follow under 200 rev/mins mixing speed, the ethyl orthosilicate of slow Dropwise 5 ml in 2h, the pH that adds the ammonia regulator solution simultaneously is 10.After continuing stirring reaction 3h, the reactant deposition is taken out; And with distilled water 3～5 times to neutral, the reuse dehydrated alcohol cleans, can obtain mean diameter behind 90～100 ℃ of oven dry 1～2h is 6 μ m, SiO
2Shell thickness is 0.5～0.8 μ m, hud typed CaCO
3/ SiO
2The toothpaste abrasive spheroidal particle.
Take by weighing 6g PSSS and be dissolved in the 1000ml distilled water, being mixed with concentration is the PSSS solution of 6g/L.Under 600 rev/mins mixing speed, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 45ml concentration, and the pH value that adds the ammonia regulator solution is 9.0.Then under 600 rev/mins mixing speed, adding concentration again is the calcium chloride solution 45ml of 0.5mol/L; Continue agitating solution 10min, at room temperature leave standstill 48h then.Take out precipitate, filtration, with distilled water 3～5 times, 90～100 ℃ can obtain the spherical calcium carbonate particle that mean diameter is 4.5 μ m after drying 1～2h.
Take by weighing above-mentioned spherical calcium carbonate particle 5g, join in the dehydrated alcohol of 70ml, and to add concentration simultaneously be 5% cetyl trimethyl ammonium bromide aqueous solution 20ml that ultra-sonic dispersion 30min forms suspension, and in 50 ℃ water bath with thermostatic control, is incubated 10min.Then under 600 rev/mins mixing speed, in 2h, slowly drip the ethyl orthosilicate of 15ml, the pH that adds the ammonia regulator solution simultaneously is 9.0.After continuing stirring reaction 4h, the reactant deposition is taken out; And with distilled water repeatedly 3～5 times to neutral, the reuse dehydrated alcohol cleans, can obtain mean diameter behind 90～100 ℃ of oven dry 1～2h is 6 μ m, SiO
2Shell thickness is 0.5～1.0 μ m, hud typed CaCO
3/ SiO
2The toothpaste abrasive spheroidal particle.
Embodiment 5
Take by weighing 8g PSSS and be dissolved in the 1000ml distilled water, being mixed with concentration is the PSSS solution of 8g/L.Under 400 rev/mins mixing speed, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 50ml concentration, and the pH value that adds the ammonia regulator solution is 10.Then under 400 rev/mins mixing speed, adding concentration again is the calcium chloride solution 50ml of 0.5mol/L; Continue agitating solution 10min, at room temperature leave standstill 36h then.Take out precipitate, filtration, with distilled water 3～5 times, 90～100 ℃ can obtain the spherical calcium carbonate particle (Fig. 2) that mean diameter is 8.2 μ m after drying 1～2h.
Take by weighing above-mentioned spherical calcium carbonate particle 5g, join in the dehydrated alcohol of 70ml, and to add concentration simultaneously be 5% cetyl trimethyl ammonium bromide aqueous solution 20ml that ultra-sonic dispersion 30min forms suspension, and in 65 ℃ water bath with thermostatic control, is incubated 5min.Then under 400 rev/mins mixing speed, in 2h, slowly drip the ethyl orthosilicate of 15ml, the pH that adds the ammonia regulator solution simultaneously is 10.After continuing stirring reaction 3h, the reactant deposition is taken out; And with distilled water 3～5 times to neutral, the reuse dehydrated alcohol cleans, can obtain mean diameter behind 90～100 ℃ of oven dry 1～2h is 10 μ m, SiO
2Shell thickness is 0.5～1.0 μ m, hud typed CaCO
3/ SiO
2The toothpaste abrasive spheroidal particle.
Take by weighing 10g PSSS and be dissolved in the 1000ml distilled water, being mixed with concentration is the PSSS solution of 10g/L.Under 800 rev/mins mixing speed, be that the sodium carbonate liquor of 0.5mol/L is poured in the PSSS solution with 40ml concentration, and the pH value that adds the ammonia regulator solution is 10.Then under 800 rev/mins mixing speed, adding concentration again is the calcium chloride solution 40ml of 0.5mol/L; Continue agitating solution 10min, at room temperature leave standstill 30h then.Take out precipitate, filtration, with distilled water 3～5 times, 90～100 ℃ can obtain the spherical calcium carbonate particle that mean diameter is 5.1 μ m after drying 1～2h.
Take by weighing above-mentioned spherical calcium carbonate particle 10g, join in the dehydrated alcohol of 130ml, and to add concentration simultaneously be 5% cetyl trimethyl ammonium bromide aqueous solution 30ml that ultra-sonic dispersion 60min forms suspension, and in 65 ℃ water bath with thermostatic control, is incubated 10min.Then under 800 rev/mins mixing speed, in 2h, slowly drip the ethyl orthosilicate of 30ml, the pH that adds the ammonia regulator solution simultaneously is 10.After continuing stirring reaction 5h, the reactant deposition is taken out; And with distilled water 3～5 times to neutral, reuse ethanol cleans, can obtain mean diameter behind 90～100 ℃ of oven dry 1～2h is 7 μ m, SiO
2Shell thickness is 0.5～1.0 μ m, hud typed CaCO
3/ SiO
2The toothpaste abrasive spheroidal particle.
List of references
[1] Li Gang. the physicochemical property of toothpaste abrasive and common type [J], tooth body dental pulp periodontal magazine, 2003,13 (8): 465-468
[2] Wang Qin, Xu Li. the abrasiveness of dentifrice abrasives [J], toothpaste industry, 2003, (3): 17-19.
[3] Luo Wenshan. the relation [J] of abrasive and attrition value in the simple analysis toothpaste, toothpaste industry, 2004, (2): 42
[4] Jin Dalai etc. compound microsphere preparation of nano-calcium carbonate and size Control [J] thereof, Chinese Journal of Inorganic Chemistry, 2004,20 (1): 21-25
[5] thunderous etc. simple and easy synthetic [J] of monodisperse spherical calcium carbonate particle, Changshu Institute of Technology journal, 2006,20 (2): 23-27
[6] patent WO0027338
[7] patent WO9739728
[8] patent WO2003075874
[9] patent CN02115028
[10] patent CN200810033368
Claims (1)
1. hud typed CaCO
3/ SiO
2The method for preparing of toothpaste abrasive is a raw material with kayexalate, sodium carbonate, calcium chloride, dehydrated alcohol, cetyl trimethyl ammonium bromide, ethyl orthosilicate and ammonia, it is characterized in that method for preparing and step are following:
Step 1: the preparation of spherical calcium carbonate particle
(1) kayexalate is dissolved in the distilled water, being mixed with concentration is the kayexalate solution of 0.5～15g/L;
(2) under speed is 200～1000 rev/mins stirring, be that the sodium carbonate liquor of 0.5mol/L is poured in the kayexalate solution with concentration, and the pH value that adds the ammonia regulator solution is 9.0～10;
(3) under speed was 200～1000 rev/mins stirring, adding concentration again was calcium chloride solution 20～50ml of 0.5mol/L; Continue agitating solution 1～15min, at room temperature leave standstill 24～48h then and form the spherical calcium carbonate particle, take out precipitate, filtration,, dry 1～2h for 90～100 ℃ with distilled water wash 3～5 times,
Step 2: hud typed CaCO
3/ SiO
2The preparation of toothpaste abrasive
(1) takes by weighing spherical calcium carbonate particle 2～10g that step 1 prepares; Join in the dehydrated alcohol of 20～150ml; And to add concentration simultaneously be cetyl trimethyl ammonium bromide aqueous solution 5～30ml of 5%; Ultra-sonic dispersion 30～60min forms suspension, and in 50～70 ℃ water bath with thermostatic control, is incubated 1～10min;
(2) under speed is 200～1000 rev/mins stirring, in 1～2h, slowly drip the ethyl orthosilicate of 4～30ml, the pH that adds the ammonia regulator solution simultaneously is 9.0～10;
(3) continue stirring reaction 3～6h after, the reactant deposition is taken out, to neutral, the reuse dehydrated alcohol cleans, and dries 1～2h for 90～100 ℃ with distilled water wash 3～5 times, can get granularity is 5～20 μ m, SiO
2Shell thickness is 0.5～1.0 μ m, monodispersed core-shell type CaCO
3/ SiO
2The spheroidal particle of toothpaste abrasive.
Behind 12-4-6 and the examination phone whole CTAB are removed, only keep cetyl trimethyl ammonium bromide.
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| CN105131786B (en) * | 2015-08-21 | 2017-07-18 | 山东大学 | A kind of environmentally friendly anticorrosive paint, preparation method and its painting method |
| CN105609737A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation process for graphene/silicon dioxide hollow sphere/sulfur composite material |
| CN106214615A (en) * | 2016-08-29 | 2016-12-14 | 郭健华 | A kind of strong teeth powder and preparation method thereof |
| CN107349113B (en) * | 2017-06-21 | 2020-04-14 | 广州玮弘祺生物科技有限公司 | Sun-screening agent microsphere completely wrapped by silicon and preparation method thereof |
| CN109422287A (en) * | 2017-08-23 | 2019-03-05 | 范佳晨 | A kind of preparation method of calcium carbonate-silica composite powder |
| CN108714122A (en) * | 2018-06-01 | 2018-10-30 | 林承伟 | A kind of permanent tooth emulsifiable paste and preparation method thereof containing rhizoma nardostachyos |
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| CN111925731A (en) * | 2020-07-24 | 2020-11-13 | 中国科学院上海微***与信息技术研究所 | Calcium carbonate/silicon dioxide core-shell type nano composite abrasive as well as preparation method and application thereof |
| CN112059172B (en) * | 2020-09-16 | 2022-06-17 | 浙江工业大学 | SiO is carried out to micron order granule2Method of coating |
| CN112574597B (en) * | 2020-12-09 | 2021-12-24 | 珠海金鸡化工有限公司 | Preparation method of superfine heavy calcium carbonate |
| CN112708390A (en) * | 2020-12-24 | 2021-04-27 | 武汉路圣材料科技有限公司 | Waterproof high-low temperature resistant concrete planting bar adhesive |
| JP7165772B2 (en) * | 2021-03-22 | 2022-11-04 | 株式会社ジーシー | Tooth surface cleaning composition |
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