CN105079882A - Method for manufacturing hydroxyl apatite from fish scale powder - Google Patents
Method for manufacturing hydroxyl apatite from fish scale powder Download PDFInfo
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- CN105079882A CN105079882A CN201410205201.5A CN201410205201A CN105079882A CN 105079882 A CN105079882 A CN 105079882A CN 201410205201 A CN201410205201 A CN 201410205201A CN 105079882 A CN105079882 A CN 105079882A
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Abstract
The invention provides a method for manufacturing hydroxyl apatite from fish scale powder. A weight ratio of collagen in the powdery fish scale powder to the hydroxyl apatite is 1:2.3-19.0. The method includes respectively arranging the fish scale powder and water in a container, and stirring and grinding mixed liquid of the fish scale powder and the water; adding zinc oxide nano particles into the mixed liquid; continuously stirring and grinding the mixed liquid until the collagen in the fish scale powder is in a liquid gel state by means of hydrolysis; filtering the mixed liquid; drying the filtered mixed liquid; smashing lumpy semi-finished products to obtain the hydroxyl apatite. A weight ratio of the fish scale powder to the water is 1:1.5-9.0. A weight ratio of the zinc oxide nano particles to the fish scale powder is 1:5-30. The method has the advantage that the hydro apatite with antibacterial, odorless and low-price characteristics can be widely applied to various daily necessities, beauty products and biomedical materials.
Description
Technical field
The present invention relates to a kind of method making oxyhydrogen-base apatite, espespecially one utilizes fish scale powder, produces antibacterial odorless and containing the method for oxyhydrogen-base apatite of collagen protein.
Background technology
In recent years, because society is to the attention gradually of " environmental protection " and " green " idea, in the environmental protection industry of 21 century, by the subject under discussion of academia and industrial circle extensive discussions be exactly the most often, how to effectively utilize resource, especially, how to effectively utilize marine resources.For people's " collagen protein " of continuing saying it with interest the most in recent years, when in market, bummaree scales a fish in the past, fish scale disperses everywhere, because of dark, people are afraid of that fish scale is bonded on skin, not easily remove, all can shy away, bummaree is also because of the dark fish scale blocking water pipe being afraid of a large amount of accumulation, the fish scale scraped must be aimed at refuse bag, and dare not directly by fish scale scraper water inlet pipe, and when closing, still must clear up the fish scale that table top is scattered and detritus, otherwise, these unremarkable fish scales still can the next day give out a foul smell, such situation, though the general impression being people to traditional fish market in the past, but do not expect, fish scale is unexpectedly in water generation today skill industrial field, one jumps and becomes the raw material making high price collagen protein, make originally by the fish scale as worn-out shoes looked, nowadays but change one's identity suddenly and become the dotey that industrial circle falls over each other recycling.
On the skin of most of Fish, be all coated with one deck by the calcareous tough and tensile ectoskeleton formed, that is exactly the derivant of fish scale, scale or scale.Fish scale accounts for the 1-5% of fish body gross weight, is a kind of multi-functional tissue, except having camouflage, maintaining except the effect of fish body profile, also has protection fish body and avoids microorganism encroach with the effect of resist the disease.Due to, different fingerling is not identical to context adaptive capacity, cause the situation that its fish body presents also to be not quite similar, wherein, the fish scale of some fingerling is obviously easily shown in (as: Ctenopharyngodon idellus, Hypophthalmichthys molitrix etc.), some fingerling but only manifests fish scale (as: Acipenser Sinensis etc.) on the top layer of certain partial skin, some fingerling is then because fish scale is very thin and wrapped (as: Monopterus albus (Zuiew)) by mucus, and be not easy to be found by common people, the fish scale of some fingerling then degenerates (as: Silurus asotus fish) completely, but, these are not worth completely and not tractable fish scale in the idea of common people, but containing the collagen protein (collagen) of 45% and the oxyhydrogen-base apatite (Hydroxy-Apatite of 55% in its main component, be called for short HAp), wherein, collagen protein is a kind of water-insoluble, threadiness is containing glycoprotein, molecular weight is about 283, 000Da, be about 300 nanometers, diameter about 1.5 nanometer, containing the triple helix structure of combining closely formed by three polypeptide chains, as shown in Figure 1, it is the key protein forming tissue.Generally speaking, collagen protein accounts for 1/3 of human body protein total amount, mainly be distributed in connective tissue, the substrate forming skeleton, cartilage, blood vessel, skin etc., collagen protein in human body can synthesize hypertrophy by the fibroblast of skin corium, but along with the age increases and the generation of free radical, the structure of collagen protein can change, and run off gradually, and the collagen protein of every annual meeting loss about 1% in normal human, thus make the outward appearance of skin can with advancing age, produce the catabiosis such as lax, wrinkle, oxyhydrogen-base apatite is a kind of calcium phosphate compound, also be the main inorganic composition of human body or animal skeleton and tooth, 60-70% is accounted in skeleton, in the enamel and ivory of tooth structure, also 90% and 70% is occupied respectively, due to, the micro-pore that grain properties in oxyhydrogen-base apatite and these intercrystallines are formed, oxyhydrogen-base apatite can be made to have good biological affinity to skeleton, calcific function is had again to tooth, in addition, also because it has good biological activity, so, clinically, be widely used on raw doctor's material of orthopaedics and dental, as: artificial bone-head, artificial tooth, os osseum patchery, artificial joint etc.
As mentioned above, due to the composition of the collagen protein and oxyhydrogen-base apatite in fish scale with high-load, make fish scale in effective utilization of waste of aquatic, be acknowledged as current surcharge the highest, the maritime function of also the most worth exploitation keeps healthy new material.For the effective recycling of fish scale, fish scale can be made into following three class finished products:
(1) fish scale powder: be fish scale is pulverized make, owing to containing natural, healthy collagen protein and oxyhydrogen-base apatite in its composition, and because of many research confirmations, can not rejection be produced for the mankind or other animal, there is biocompatibility, edible safety, and have no side effect, therefore in Japan, fish scale powder is used as healthy accesary foods, and according to functional with patent classification, is classified as a kind of stratum corneum promoter; At TaiWan, China, the test of agricultural commission of Executive Yuan Aquatic product research worker effort under, the particle diameter of fish scale powder can be crushed to 0.074mm, and its technical fish scale powder (only 18.8% particle diameter is less than 1mm) be better than obtained by Japan Patent (special permission P2004-59568A), therefore, fish scale powder at present by many industries be applied to make in health food, dietary supplement, health-care feed and the product such as dehumidifying, aromatic the basic material that uses.
(2) scale collagen victory peptide: the collagen protein in fish scale, it is the main constituent maintaining skin and the elasticity of muscle, but its topmost glamour still has the magical usefulness of " aging resistance ", effectively can improve the problems such as elasticity of skin, microgroove and pore be careful, at present, commercially available aging-resistant is cured in U.S. skin care products and is nearly all added collagen protein, in the application of other side, also just like the functional food and the animal feed that prevent skin aging in order to making described in Japan Patent (JP 2000-247894); As described in Japan Patent (Unexamined Patent 10-231250) in order to make the agent of osteoporosis disease; The health food in order to make hair hair quality and improving gloss as described in Japan Patent (Unexamined Patent 10-155428); And the function health food in order to make pressure of releiving as described in Japan Patent (JP 2005-306761); These application above-mentioned all show, containing the fish scale powder of collagen protein except there is U.S. flesh, osteoporosis disease, relaxing arthritis, controlling except the function such as to ache, also have improve color development, the effects such as pressure of releiving.At present, the collagen protein that TaiWan, China face beautifying health keeping product market uses, except minority manufacturer lays claim to except manufacturing capacity, about 90% all from abroad, and commercially available collagen protein raw material is mostly made from the extraction of the animal tissue such as cattle,pig and sheep, avian species, this phenomenon, not only show TaiWan, China related industry and there is the unstable secret worry of the collagen protein supply of material all the time, and after in succession breaking out the epidemic situations such as mad cow syndrome, foot and mouth disease and bird flu, commercially available collagen protein is no longer subject to trust and the favor of ordinary consumer.In view of this, many Sheng Ji manufacturers transfer research and extract collagen protein from other biologicals, and the collagen protein because containing 45% in fish scale, therefore, make fish scale suddenly become the rising star in collagen protein market.But, because 3 bursts of helical polypeptide chain structures of collagen protein directly cannot pass through skin barrier, therefore when it can be used as the composition of skin care products, only there is moisture-keeping functions, and the fibroblast of skin corium cannot be activated, and then promote the synthesis hypertrophy of collagen protein, make skin have elasticity as advertisement.Therefore, collagen protein must nanorize and by carrier, or be hydrolyzed into short chain victory peptide via appropriateness, skin barrier could be passed through smoothly and arrive at skin corium, but, because its technique is rather numerous and diverse, very accurate and do not meet environmental protection concept, cause collagen protein amylase per kilogram commercially available at present up to about New Taiwan Currency more than 10,000 yuan, also because manufacturing cost is too high, and economic worth is lost.
(3) fish scale oxyhydrogen-base apatite: oxyhydrogen-base apatite is main constituent remaining extract collagen protein in fish scale after, because it has good biological affinity to skeleton, calcific function is had again to tooth, there is good biological activity, be widely used the raw doctor's material as orthopaedics and dental clinically, but, with the amylase of aforementioned collagen protein, also because the technique of its refine is rather numerous and diverse, very accurate and do not meet environmental protection concept, the price causing it current is also about New Taiwan Currency 8-15 ten thousand yuan up to per kilogram.In addition, due to the exfoliator that oxyhydrogen-base apatite is also pure natural, gentleness, physical property, can in order to remove aging cutin layer, make skin smooth, and skin acid value can not be destroyed, be well suited for being applied in the daily living article such as bath oil, clean skin soap, also can be used as the grinding agent in health-care toothpaste, the materials such as dental surface pigment, white macula, dental plaque can not only be removed, also to the microlesion on tooth, there is certain mending function, to strengthen tooth sclerotin.
In addition, statistics according to Aquatic product test institute of TaiWan, China Executive Yuan agricultural commission shows, TaiWan, China about produces the fish scale of 3-4 ten thousand tonnes every year, utilize if can do it comprehensively and effectively, not only can realize the object reducing garbage, also can give full play to an economic benefit of squama Cheng Jin, make originally unremarkable processing waste, become valuable processing base material, be widely used in make face beautifying health keeping product, health food and medical science and give birth to and cure on material.But, in the process extracting the main constituent such as collagen protein and oxyhydrogen-base apatite in fish scale powder, its main key technology how to utilize precision and the scientific method of miniaturization and technique, get rid of the weed and keep the flower of the leek, make aforementioned functional composition in fish scale powder can under the condition of noresidue medicine or heavy metal, and not containing under fishlike smell and non-perishable prerequisite, be extracted out.Especially, the fish scale powder of general drying and crushing commercially available is at present because winning peptide containing a large amount of scale collagens, therefore be all not easily ground into fine Powdered, and mostly in flocculence, not only cause oxyhydrogen-base apatite granule wherein larger, and scale collagen victory peptide is wherein because having fishlike smell and putrefactive shortcoming, causes it and cannot be widely used in all the time on making daily living article, face beautifying health keeping product and raw doctor's material.
The fish scale oxyhydrogen-base apatite of the Taiwan Channa argus (" Tilapia " that be namely commonly called as) producing for TaiWan, China fertilizer limited company (i.e. " platform is fertile ") institute and sell, though its unit price only per kilogram is about New Taiwan Currency 1, 000 yuan, but, because of its not with superprecision and the refinement step of miniaturization make, cause wherein still containing scale collagen victory peptide, except tool fishlike smell, also very easily stink because of corrupt, so, how to be apt to this inexpensive raw material, utilize simple and easy and efficient technique, with a skill and technique of squama Cheng Jin, be translated into and can be widely used in making daily living article, face beautifying health keeping product and life are cured on material, namely the important topic that the present invention inquires in this wish is become.
Summary of the invention
As mentioned above, refine oxyhydrogen-base apatite in fish scale powder at present, must pass through above-mentioned numerous and diverse and very accurate refinery practice, not only be not inconsistent environmental protection concept, and because of manufacturing cost too high, cause fetch long price, and generally cannot be applied in daily living article, face beautifying health keeping product and life are cured in material, the precious characteristic making it have (as: has good biological affinity to skeleton, calcific function is had again to tooth, there is good biological activity, also be pure natural, gentle, physical property and the exfoliator of skin acid value can not be destroyed) cannot be fully utilized, and, because the organic component in collagen protein in fish scale powder has fishlike smell and easy corrupt smelly characteristic, also the inexpensive fish scale powder causing TaiWan, China to be produced so far still only can by as animal feed, and fully cannot be used in daily living article, the field of face beautifying health keeping product and raw doctor's material.In view of this, inventor relies on the individual professional scholarship and self-cultivation at biochemistry and experience, through long-term endeavour research and experiment, finally development and Design goes out of the present inventionly a kind ofly to utilize fish scale powder to make antibacterial odorless and containing the method for oxyhydrogen-base apatite of collagen protein, phase makes its manufactured goods energy because possessing the characteristic of antibacterial odorless and cheap price, and be widely used in various daily living article, face beautifying health keeping product and raw doctor's material, to benefit consumers in general, and implement the final environmental protection demand reducing garbage.
The object of this invention is to provide a kind of method utilizing fish scale powder to make oxyhydrogen-base apatite, wherein, described fish scale powder is in dry powdery, in described fish scale powder, the weight ratio of collagen protein and oxyhydrogen-base apatite (i.e. hydroxyapatite) is 1:2.3-19.0, the method inserts in a container respectively by described fish scale powder and water, again with high compactness zirconium oxide bead, the fish scale powder of container bottom deposition is ground, wherein, the weight ratio of described fish scale powder and water is 1:1.5-9.0;
In described mixed liquor, add zinc oxide nano-particle, wherein, the weight ratio of zinc oxide nano-particle and fish scale powder is 1:5-30;
Continue to stir mixed liquor and grind, until the collagen hydrolysate in described fish scale powder becomes liquid colloidal, to make described mixed liquor be thick, and make the oxyhydrogen-base apatite in described fish scale powder and zinc oxide nano-particle evenly and be suspended in described mixed liquor dispersedly;
Described mixed liquor is filtered, with filtering zirconium oxide bead wherein and other impurity;
The described mixed liquor completing filtration is inserted a baking oven, by baking oven, drying and processing is carried out to described mixed liquor, with the semi-finished product making the drying of described mixed liquor become caking shape, and make original evenly and the zinc oxide nano-particle be suspended in dispersedly in the collagen protein of thick liquid state, between the triple helix structure infiltrating collagen protein, and with collagen protein be together coated on dryly oxyhydrogen-base apatite surface and on hole in, form a collagen film, now, because zinc oxide nano-particle itself is photocatalyst, have and realize mycete, the organic Degradations such as antibacterial and virus, and kill mycete, the function of antibacterial and virus, and make described collagen film become antibacterial film, possess and undergo no deterioration, corrupt and smelly characteristic,
Finally, the semi-finished product of caking shape are inserted a pulverizer, and utilizes pulverizer to carry out pulverization process to semi-finished product, be ground into the oxyhydrogen-base apatite powder of less than 1 micron size, produce manufactured goods of the present invention.
In method of the present invention, preferably, the method also comprises silver salt powder, with a predetermined percentage by weight, be added in an aqueous solution, and to described aqueous solution uniform stirring, can be uniformly dispersed in aqueous solution to make described silver salt powder, and make described aqueous solution remain on the first temperature, described aqueous solution is by water, the composition such as alkali liquor and ammonia, according to predetermined percentage by weight, Homogeneous phase mixing forms, described alkali liquor is in order to transform into silver hydroxide by silver salt, because silver hydroxide can form brown precipitate in aqueous, cannot be evenly dispersed in aqueous solution, therefore also must add ammonia in aqueous, with the precipitation by silver hydroxide, be ionized into as ammonification silver complex ion,
Described oxyhydrogen-base apatite powder is inserted a baking oven and is baked to the second temperature, wherein, described second temperature is greater than described first temperature;
Described oxyhydrogen-base apatite powder is immersed in described aqueous solution, carry out the stirring of a scheduled time, making can because of action of thermal difference between the hole of dense distribution on described oxyhydrogen-base apatite powder surface and aqueous solution, and produce osmotic effect, described aqueous solution is made to be able to via these holes, successfully infiltrate surface and the internal void of described oxyhydrogen-base apatite powder, and make ammonification silver complex ion can infiltrate these holes along with described aqueous solution;
Then, formaldehyde or the glucose of a predetermined weight percent is added in described aqueous solution, and continue stirring one scheduled time, make formaldehyde or glucose the surface and intrapore ammonification silver complex ion thereof of infiltrating described oxyhydrogen-base apatite powder can be reduced into Nano silver grain;
Described oxyhydrogen-base apatite powder is taken out in described aqueous solution, carry out high temperature drying process, with after described oxyhydrogen-base apatite powder bone dry, make the Nano silver grain in these holes by the described collagen protein of described oxyhydrogen-base apatite powder surface institute coating, on the surface being stably attached to described oxyhydrogen-base apatite powder and in hole, form the nanoparticle composite membrane of tool zinc oxide and silver, the weight ratio of wherein said zinc oxide nano-particle and Nano silver grain, take 5-60:1 as the best, and it is antibacterial to make described oxyhydrogen-base apatite powder possess long-acting type, sterilization and antiseptical effect.
In method provided by the present invention, preferably, the temperature difference of the second temperature and the first temperature is 20 DEG C-80 DEG C.
In method provided by the present invention, preferably, the second temperature of described oxyhydrogen-base apatite powder is less than 250 DEG C.
In method provided by the present invention, preferably, the first temperature of described aqueous solution is room temperature or low temperature, i.e. 10-25 DEG C, and the second temperature of described oxyhydrogen-base apatite powder is 30-105 DEG C.
In method provided by the present invention, preferably, the silver salt powder adopted is water miscible silver salt powder; More preferably, described silver salt powder comprises silver nitrate or silver acetate.
In method provided by the present invention, preferably, the alkali liquor adopted comprises potassium hydroxide or sodium hydroxide.
In method provided by the present invention, preferably, in described aqueous solution, the percentage by weight of water is 80%-99%, in described aqueous solution, the percentage by weight of alkali liquor is 0.001%-5%, the percentage by weight of described Ammonia In Aqueous Solution water is 0.005%-25%, and the percentage by weight of described formaldehyde in aqueous solution or glucose is respectively 0.001%-0.05% or 0.002%-0.1%.
The antibacterial odorless of oxyhydrogen-base apatite that the method utilizing fish scale powder to make oxyhydrogen-base apatite provided by the invention is obtained and be rich in collagen protein, phase makes its manufactured goods energy because possessing the characteristic of antibacterial odorless and cheap price, and be widely used in various daily living article, face beautifying health keeping product and raw doctor's material, to benefit consumers in general, and implement the final environmental protection demand reducing garbage.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the triple helix structure of collagen protein under micro state;
Fig. 2 is the processing technology schematic diagram of a preferred embodiment of the present invention; And
Fig. 3 is the processing technology schematic diagram of another preferred embodiment of the present invention.
Detailed description of the invention
For just to the object, the technical characteristics and the effect of the present invention, further understanding and understanding can be had, here especially exemplified by an embodiment, and coordinate graphic, be described in detail as follows:
Zinc oxide nano-particle because of its crystallite dimension and light wave quite or less, dimensional effect causes the interval of its conduction band and valence band to increase, its light absorpting ability is significantly strengthened, therefore, under light illumination, when one has the photon of certain energy, or there is the photon exceeding quasiconductor band-gap energy, when injecting the semiconducting electonic structure of zinc oxide nano-particle, an electrons in semiconducting crystal is from valence to conduction band, the next one is stayed to have the positively charged hole of powerful oxidability, as the hydrone (H in hole and water and air
2when O) meeting, photochemical reaction can be passed through, grab the electronics of hydroxy in hydrone, now, the hydroxy losing electronics becomes non-persistent hydroxyl free radical (OH) at once, non-persistent hydroxyl free radical is once run into Organic substance that is external or that be attached on zinc oxide nano-particle, can by grabbing the mode of the other side's electronics, make oneself to tend towards stability, like this, these Organic substances and oxidized, and become water and carbon dioxide, be dissipated in water and air, therefore zinc oxide nano-particle can as photocatalyst, realize mycete, the organic degradeds such as antibacterial and virus, to kill mycete, antibacterial and virus.Described in upper, zinc oxide nano-particle really can under the environment having light, possess long-acting type antibacterial, sterilize, can not develop immunity to drugs, the plurality of advantages such as avirulence, non-stimulated anaphylaxis and the impact of acid and alkali base number.
Embodiment 1
A preferred embodiment of the present invention, refer to shown in Fig. 2, it is the above-mentioned characteristic utilizing zinc oxide nano-particle, zinc oxide nano-particle is applied in method of the present invention, the fish scale powder used in the present embodiment is in dry powdery, and the weight ratio of collagen protein and oxyhydrogen-base apatite (i.e. hydroxyapatite) is 1:2.3-19.0 in fish scale powder, namely collagen protein and the oxyhydrogen-base apatite percentage by weight in fish scale powder is at 30%:70%-5%:95%, and the method comprises the following steps:
Fish scale powder and water are inserted in a container by 201 respectively, and the mixed liquor of the two is stirred and ground, as: with high compactness zirconium oxide bead, the fish scale powder of container bottom deposition is ground, wherein, the weight ratio of fish scale powder and water is 1:1.5-9.0, and namely fish scale powder and water percentage by weight in mixed liquor is 40:60%-10%:90%;
202 add zinc oxide nano-particle in mixed liquor, in the present embodiment, it is the particle first zinc oxide being ground to form nanometer (nanometer) size, 1 nanometer equals 1/1000000000th meter (10-9meter), or the particle of nanoscale size, namely be about 1-100 nanometer, the nanoparticle between molecule and secondary micron, and the weight ratio of zinc oxide nano-particle and fish scale powder is 1:5-30;
203 continue to stir mixed liquor and grind, until the collagen hydrolysate in fish scale powder becomes liquid colloidal, to make mixed liquor be thick, and make the oxyhydrogen-base apatite in fish scale powder and zinc oxide nano-particle evenly and be suspended in dispersedly in mixed liquor;
204 pairs of mixed liquors filter, with filtering impurity wherein, as zirconium oxide bead and other impurity;
The mixed liquor completing filtration is inserted a baking oven by 205, through baking oven, drying and processing is carried out to mixed liquor, with the semi-finished product making mixed liquor drying become caking shape, and make oxyhydrogen-base apatite in semi-finished product after bone dry, original evenly and the zinc oxide nano-particle be suspended in dispersedly in the collagen protein of thick liquid state, between the triple helix structure infiltrating collagen protein, and with collagen protein be together coated on dryly oxyhydrogen-base apatite surface and on hole in, form a collagen film, now, because zinc oxide nano-particle itself is photocatalyst, have and realize mycete, the organic Degradations such as antibacterial and virus, and kill mycete, the function of antibacterial and virus, and make collagen film become antibacterial film, possess and undergo no deterioration, corrupt and smelly characteristic,
206 is last, the semi-finished product of caking shape inserted a pulverizer, utilizes pulverizer to carry out pulverization process to semi-finished product, be ground into the oxyhydrogen-base apatite powder of 1 μm of (micron) following size, namely produce manufactured goods of the present invention.
Like this, namely oxyhydrogen-base apatite powder of the present invention by the structural zinc oxide nano-particle of triple helix of the collagen protein of institute's coating on it, under the state having light, realizes organic antibacterial and sterilization effects such as antibacterial, virus and mycetes.
In addition, Nano silver grain is because of fine particles, whole surface area is significantly increased, active change is large, very easily discharge active silver ion, to attract the sulfydryl in bacterial body on pheron, and be combined rapidly with it, ferment containing sulfydryl is lost activity, cause bacterial death, and positively charged silver ion is after touching electronegative microbial cell, can mutually adsorb, the mantle of puncture microorganism, make inside microbes degeneration, reduce energy for growth, allow cell cannot metabolism and breeding, until dead, in addition, after antibacterial is killed by silver ion, silver ion again can be free out from the antibacterial die, continue the action other antibacterial that lives being cooked to repetition, until all antibacterials are eliminated, therefore Nano silver grain need not activate in illumination, namely there is excellent antibacterial and sterilization effect, more can grow by mould fungus inhibition, effectively reach anti-corrosion function, and can not develop immunity to drugs, and there is avirulence, the plurality of advantages such as non-stimulated anaphylaxis and the impact of acid and alkali base number.
In another preferred embodiment of the present invention, consult shown in Fig. 3, in order to ensure oxyhydrogen-base apatite powder under unglazed environment, still can produce the antibacterial and sterilization effect of long-acting type, Nano silver grain is applied to preceding method by the present invention further, and the method also comprises the following steps:
301 by silver salt powder, as silver nitrate (AgNO
3) and silver acetate (CH
3cOOAg) etc., with a predetermined percentage by weight, be added in an aqueous solution, and to aqueous solution uniform stirring, can be uniformly dispersed in aqueous solution to make silver salt powder, and make aqueous solution remain on the first temperature, aqueous solution is that according to predetermined percentage by weight, Homogeneous phase mixing forms by compositions such as water, alkali liquor (as KOH or NaOH aqueous solution) and ammonia (or ammonia), this alkali liquor is according to following chemical formula, by silver salt as silver nitrate (AgNO
3) transform into silver hydroxide (AgOH):
AgNO
3(aq)+KOH
(aq)→AgOH
(ppt)+K
++NO
3 -
Because silver hydroxide can form brown precipitate in aqueous, cannot be evenly dispersed in aqueous solution, therefore also must add ammonia (or ammonia) in aqueous, to comply with following chemical formula, by the precipitation of silver hydroxide (AgOH), be ionized into as ammonification silver complex ion (Ag (NH
3)
2 +):
AgOH
(ppt)+2NH
4OH
(aq)→Ag(NH
3)
2 + (aq)+OH
-+2H
2O
Oxyhydrogen-base apatite powder is inserted a baking oven by 302 is baked to the second temperature, and wherein the second temperature must be less than 250 DEG C, and need be greater than the first temperature, and the temperature difference is 20-80 DEG C;
Oxyhydrogen-base apatite powder immerses in aqueous solution by 303, carry out the stirring of a scheduled time, making can because of action of thermal difference between oxyhydrogen-base apatite powder and aqueous solution, and produce osmotic effect, make aqueous solution successfully be infiltrated through the surface of oxyhydrogen-base apatite powder and the hole of inner dense distribution, make ammonification silver complex ion can infiltrate these holes along with aqueous solution;
304 formaldehyde (HCHO) or the glucoses adding a predetermined weight percent in aqueous, and continue stirring one scheduled time, make formaldehyde (HCHO) or glucose to comply with following chemical formula, will the intrapore ammonification silver complex ion (Ag (NH of oxyhydrogen-base apatite powder be infiltrated
3)
2 +), be reduced into Nano silver grain (Ag (ppt)):
2Ag(NH
3)
2 + (aq)+HCHO
(l)+2OH
-→2Ag
(ppt)+HCOO
-+NH
4 ++3NH
3(g)+H
2O
Oxyhydrogen-base apatite powder takes out by 305 in aqueous solution, carry out high temperature drying process, with after oxyhydrogen-base apatite powder bone dry, make on the surface of oxyhydrogen-base apatite powder and intrapore Nano silver grain, by the collagen protein of the surperficial institute coating of oxyhydrogen-base apatite powder, on the surface being stably attached to oxyhydrogen-base apatite powder and in hole, and on the surface of oxyhydrogen-base apatite powder and form the nanoparticle composite membrane of a zinc oxide and silver in hole.
In previous embodiment of the present invention, aqueous solution is that according to following percentage by weight, Homogeneous phase mixing forms by compositions such as water, silver nitrate and/or silver acetate, alkali liquor (as: KOH or NaOH aqueous solution) and ammonia:
(1) water: as deionized water or pure water etc., its percentage by weight is 80%-99%;
(2) water miscible silver salt powder: as: silver nitrate (AgNO
3) and silver acetate (CH
3cOOAg) etc., its percentage by weight is 0.001%-5%, and water soluble silver salt powder has and is dissolvable in water aqueous solution, and discharges the characteristic of ammonification silver complex ion in aqueous;
(3) alkali liquor: the aqueous solution of potassium hydroxide or sodium hydroxide, its percentage by weight is 0.001%-5%, in the process stirred aqueous solution, silver salt can be transformed into silver hydroxide; And
(4) ammonia (or ammonia): its percentage by weight is 0.005%-25%, in the process stirred aqueous solution, can change into ammonification silver complex ion [Ag (NH by the precipitating ion of silver hydroxide
3)
2 +], because, ammonification silver complex ion has the characteristic of oxyphie, thus very easily with the oxygen bond on zinc oxide nano-particle, and in the modulated process of aqueous solution, be attached to the surface of zinc oxide nano-particle equably.
In the above-described embodiments, first temperature of aqueous solution can be room temperature or low temperature, i.e. 10-25 DEG C, second temperature of oxyhydrogen-base apatite powder, be then 30-105 DEG C, the temperature difference of the two remains on 20-80 DEG C, when oxyhydrogen-base apatite powder is dumped in aqueous solution, when carrying out the whipping process of at least ten minutes, can because of action of thermal difference between oxyhydrogen-base apatite powder and aqueous solution, and produce osmotic effect, make aqueous solution successfully can infiltrate the surface of oxyhydrogen-base apatite powder and the hole of inner dense distribution, air in these holes is extruded, so, in whipping process, to emerge in aqueous many small bubbles, and then make ammonification silver complex ion can infiltrate these holes along with aqueous solution, then, add formaldehyde (HCHO) or 0.002%-0.1% glucose (C that percentage by weight is 0.001%-0.05% in aqueous
6h
12o
6h
2o), and continue to stir at least 30 minutes, make formaldehyde or glucose can infiltrate in the hole of oxyhydrogen-base apatite powder, and with the ammonification silver complex ion generation chemical reaction in it, ammonification silver complex ion is made to be reduced into Nano silver grain, and be firmly attached on the surface of zinc oxide nano-particle, finally, oxyhydrogen-base apatite powder is taken out in aqueous solution, insert a baking oven, and by baking oven, drying and processing is carried out to oxyhydrogen-base apatite powder, after oxyhydrogen-base apatite powder bone dry, on the surface of oxyhydrogen-base apatite powder and intrapore zinc oxide nano-particle and Nano silver grain, namely by the collagen protein of the surperficial institute coating of oxyhydrogen-base apatite powder, on the surface being stably attached to oxyhydrogen-base apatite powder and in hole, form the nanoparticle composite membrane of a zinc oxide and silver.
In above-mentioned preferred embodiment of the present invention, through repeatedly testing proof, zinc oxide nano-particle in nanoparticle composite membrane and the percentage by weight between Nano silver grain are 5:1-60:1, can produce best antibacterial and sterilization effect to Organic substances such as antibacterial, virus and mycetes.
The above, be only a best specific embodiment of the present invention, but feature of the present invention is not limited thereto, and is anyly familiar with this those skilled in the art in field of the present invention, can think easily and change or modification, all should be encompassed in above right of the present invention.
Claims (10)
1. utilize fish scale powder to make a method for oxyhydrogen-base apatite, wherein, described fish scale powder is in dry powdery, and in described fish scale powder, the weight ratio of collagen protein and oxyhydrogen-base apatite is 1:2.3-19.0, and the method comprises:
Described fish scale powder and water are inserted respectively in a container, and stir the mixed liquor of the two and grind, wherein, the weight ratio of described fish scale powder and water is 1:1.5-9.0;
In described mixed liquor, add zinc oxide nano-particle, the weight ratio of described zinc oxide nano-particle and fish scale powder is 1:5-30;
Continue to stir described mixed liquor and grind, until the collagen hydrolysate in described fish scale powder becomes liquid colloidal, to make described mixed liquor be thick, and described oxyhydrogen-base apatite and zinc oxide nano-particle is made evenly and to be dispersedly suspended in mixed liquor;
Described mixed liquor is filtered, with the impurity in filtering mixed liquor;
The mixed liquor completing filtration is inserted a baking oven, drying and processing is carried out to described mixed liquor, with the semi-finished product making the drying of described mixed liquor become caking shape, and make oxyhydrogen-base apatite in described semi-finished product after bone dry, original evenly and the zinc oxide nano-particle be suspended in dispersedly in the collagen protein of thick liquid state, can with collagen protein be together coated on dryly oxyhydrogen-base apatite surface and on hole in, form a collagen film; And
The semi-finished product of caking shape are inserted a pulverizer, pulverization process is carried out to described semi-finished product, described semi-finished product is ground into the oxyhydrogen-base apatite powder of less than 1 micron size.
2. method according to claim 1, the method also comprises:
By silver salt powder with a predetermined percentage by weight, be added in an aqueous solution, and to described aqueous solution uniform stirring, to make described silver salt powder can be uniformly dispersed in described aqueous solution, and make described aqueous solution remain on the first temperature, described aqueous solution is according to predetermined percentage by weight by water, alkali liquor and ammonia, Homogeneous phase mixing forms, so that silver salt is transformed into silver hydroxide, and recycling ammonia, by the precipitation of silver hydroxide, be ionized into as ammonification silver complex ion;
Described oxyhydrogen-base apatite powder is inserted a baking oven and is baked to the second temperature, wherein, described second temperature is greater than described first temperature;
Described oxyhydrogen-base apatite powder is immersed in described aqueous solution, carry out the stirring of a scheduled time, make between described oxyhydrogen-base apatite powder and aqueous solution because of action of thermal difference, and produce osmotic effect, make described aqueous solution infiltrate the surface of described oxyhydrogen-base apatite powder and the hole of inner dense distribution, make described ammonification silver complex ion infiltrate in described hole along with described aqueous solution;
In described aqueous solution, add formaldehyde or the glucose of a predetermined weight percent, and continue stirring one scheduled time, make described formaldehyde or glucose the intrapore ammonification silver complex ion infiltrating described oxyhydrogen-base apatite powder can be reduced into Nano silver grain; And
Described oxyhydrogen-base apatite powder is taken out in described aqueous solution, carry out high temperature drying process, with after described oxyhydrogen-base apatite powder bone dry, make the zinc oxide nano-particle in hole and Nano silver grain by the collagen protein of its surperficial institute coating, on the surface being together stably attached to described oxyhydrogen-base apatite powder and in hole, and on the surface of described oxyhydrogen-base apatite powder and form the nanoparticle composite membrane of a zinc oxide and silver in hole.
3. method according to claim 2, wherein, the zinc oxide nano-particle in described nanoparticle composite membrane and the weight ratio of Nano silver grain are 5-60:1.
4. method according to claim 3, wherein, with high compactness zirconium oxide bead, grinds the fish scale powder of container bottom deposition.
5. method according to claim 4, wherein, the temperature difference of described second temperature and described first temperature is 20 DEG C-80 DEG C.
6. method according to claim 5, wherein, the second temperature of described oxyhydrogen-base apatite powder is less than 250 DEG C.
7. method according to claim 6, wherein, the first temperature of described aqueous solution is room temperature or low temperature, i.e. 10-25 DEG C, and the second temperature of described oxyhydrogen-base apatite powder is 30-105 DEG C.
8. method according to claim 7, wherein, described silver salt powder is silver nitrate or silver acetate.
9. method according to claim 8, wherein, described alkali liquor comprises potassium hydroxide or sodium hydroxide.
10. method according to claim 9, wherein, in described aqueous solution, the percentage by weight of water is 80%-99%, in described aqueous solution, the percentage by weight of alkali liquor is 0.001%-5%, the percentage by weight of described Ammonia In Aqueous Solution water is 0.005%-25%, and the percentage by weight of described formaldehyde in aqueous solution or glucose is respectively 0.001%-0.05% or 0.002%-0.1%.
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| CN106430134A (en) * | 2016-09-05 | 2017-02-22 | 东南大学 | Silver and zinc oxide double phase sediment hydroxyapatite nanometer material and preparation method thereof |
| CN112175577A (en) * | 2020-11-24 | 2021-01-05 | 佛山市高建硅胶实业有限公司 | Silicone structural adhesive and preparation method thereof |
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