TWI787091B - Oyster shell powder and manufacture method thereof - Google Patents
Oyster shell powder and manufacture method thereof Download PDFInfo
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- TWI787091B TWI787091B TW111106745A TW111106745A TWI787091B TW I787091 B TWI787091 B TW I787091B TW 111106745 A TW111106745 A TW 111106745A TW 111106745 A TW111106745 A TW 111106745A TW I787091 B TWI787091 B TW I787091B
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- zinc
- oyster shell
- shell powder
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 275
- 239000000843 powder Substances 0.000 title claims abstract description 249
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 276
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 274
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 274
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000654 additive Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 239000011787 zinc oxide Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 150000003751 zinc Chemical class 0.000 claims description 46
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 37
- 239000000194 fatty acid Substances 0.000 claims description 37
- 229930195729 fatty acid Natural products 0.000 claims description 37
- -1 fatty acid compound Chemical class 0.000 claims description 28
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000292 calcium oxide Substances 0.000 claims description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 73
- 238000012360 testing method Methods 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 235000014692 zinc oxide Nutrition 0.000 description 33
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 239000011667 zinc carbonate Substances 0.000 description 25
- 235000004416 zinc carbonate Nutrition 0.000 description 25
- 229910000010 zinc carbonate Inorganic materials 0.000 description 25
- 239000002245 particle Substances 0.000 description 22
- 235000021355 Stearic acid Nutrition 0.000 description 21
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 21
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 21
- 239000008117 stearic acid Substances 0.000 description 21
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 241000237502 Ostreidae Species 0.000 description 15
- 235000020636 oyster Nutrition 0.000 description 15
- 150000004665 fatty acids Chemical class 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 241000894006 Bacteria Species 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000010903 husk Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 241000736199 Paeonia Species 0.000 description 7
- 235000006484 Paeonia officinalis Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 235000012054 meals Nutrition 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 4
- 229940007718 zinc hydroxide Drugs 0.000 description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
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- 235000001674 Agaricus brunnescens Nutrition 0.000 description 2
- 241000237519 Bivalvia Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- HQYUWCXFCCIKPT-UHFFFAOYSA-J dizinc octadecanoate Chemical compound [Zn++].[Zn++].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQYUWCXFCCIKPT-UHFFFAOYSA-J 0.000 description 1
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- 235000013312 flour Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical compound COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ZIVWJFMRHVQHCV-UHFFFAOYSA-N zinc;oxygen(2-);hydrate Chemical group O.[O-2].[Zn+2] ZIVWJFMRHVQHCV-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/26—Carbonates; Bicarbonates
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- C08K9/00—Use of pretreated ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
Description
本揭示內容的一些實施方式中涉及含鋅牡蠣殼粉及其製備方法，特別是一種提升抗菌效果以及抗菌耐水性(為經水洗後的抗菌性)的含鋅牡蠣殼粉及其製備方法。 Some embodiments of the present disclosure relate to zinc-containing oyster shell powder and its preparation method, especially a zinc-containing oyster shell powder with improved antibacterial effect and antibacterial water resistance (antibacterial property after washing), and its preparation method.
牡蠣為台灣甚至各國的美食之一，然而牡蠣食用後留下的廢棄牡蠣殼不易分解處理，長久累積會破壞生態環境，並產生惡臭。 Oysters are one of the delicacies in Taiwan and even other countries. However, the discarded oyster shells left after eating oysters are not easy to decompose, and long-term accumulation will damage the ecological environment and produce foul odors.
牡蠣殼富含碳酸鈣，若對牡蠣殼執行煅燒處理，再將煅燒後的牡蠣殼研磨，可獲得經煅燒的牡蠣殼粉，其中牡蠣殼中之部分或全部的碳酸鈣，在經煅燒的牡蠣殼粉中，會轉變為氧化鈣，具有氧化鈣的經煅燒的牡蠣殼粉具有抗菌性。 Oyster shells are rich in calcium carbonate. If the oyster shells are calcined, and then the calcined oyster shells are ground, the calcined oyster shell powder can be obtained, wherein part or all of the calcium carbonate in the oyster shells is contained in the calcined oyster shells. Calcined oyster shell powder with calcium oxide has antibacterial properties.
然而，因經煅燒的牡蠣殼粉的主要成分為氧化鈣，接觸水會反應為微溶於水的氫氧化鈣，經水洗，氫氧化鈣會隨水流失，降低抗菌效果。However, because the main component of calcined oyster shell powder is calcium oxide, it will react into slightly water-soluble calcium hydroxide when it contacts water. After washing with water, calcium hydroxide will be lost with water, reducing the antibacterial effect.
因此，如何提升牡蠣殼粉的抗菌效果以及抗菌耐水性，是所欲解決的問題。Therefore, how to improve the antibacterial effect and antibacterial water resistance of oyster shell powder is a problem to be solved.
本揭示內容中的一些實施方式提供製備含鋅牡蠣殼粉的方法，包含：提供牡蠣殼粉；提供含鋅添加物；混合牡蠣殼粉與含鋅添加物，獲得混合物；以及加熱混合物，使混合物反應生成包含氧化鋅的含鋅牡蠣殼粉。Some embodiments of the present disclosure provide a method of preparing zinc-containing oyster shell powder, comprising: providing oyster shell powder; providing a zinc-containing additive; mixing the oyster shell powder and the zinc-containing additive to obtain a mixture; and heating the mixture such that the mixture The reaction produces a zinc-containing oyster shell powder that contains zinc oxide.
在一些實施方式中，含鋅添加物包含含鋅有機物、含鋅無機物或其組合。In some embodiments, the zinc-containing additive comprises a zinc-containing organic, a zinc-containing inorganic, or a combination thereof.
在一些實施方式中，混合牡蠣殼粉與含鋅添加物的步驟為乾式固態混合。In some embodiments, the step of mixing the oyster shell meal with the zinc-containing additive is dry solid state mixing.
在一些實施方式中，煅燒混合物的步驟，包含在150°C至1100°C的溫度範圍中加熱混合物。In some embodiments, the step of calcining the mixture comprises heating the mixture at a temperature ranging from 150°C to 1100°C.
在一些實施方式中，加熱混合物的步驟，包含加熱混合物至預定時間，使含鋅牡蠣殼粉中的氧化鋅呈奈米級分佈，而不會團聚為微米級以上。In some embodiments, the step of heating the mixture includes heating the mixture for a predetermined time, so that the zinc oxide in the zinc-containing oyster shell powder is distributed in a nanometer scale without agglomerating to a size above a micrometer scale.
在一些實施方式中，在煅燒混合物的步驟之後，更包含在高於脂肪酸類化合物的熔點的的溫度範圍中混合含鋅牡蠣殼粉與脂肪酸類化合物，獲得改質含鋅牡蠣殼粉。In some embodiments, after the step of calcining the mixture, further comprising mixing the zinc-containing oyster shell powder and the fatty acid compound at a temperature range higher than the melting point of the fatty acid compound to obtain a modified zinc-containing oyster shell powder.
本揭示內容中的一些實施方式提供含鋅牡蠣殼粉，包含含鈣核心以及複數含鋅奈米級粒子。含鋅奈米級粒子散佈於含鈣核心的表面，其中含鋅奈米級粒子的其中一者的晶格與含鈣核心的晶格相連。Some embodiments of the present disclosure provide zinc-containing oyster shell powder comprising a calcium-containing core and a plurality of zinc-containing nanoparticles. The zinc-containing nanoparticles are dispersed on the surface of the calcium-containing core, wherein the lattice of one of the zinc-containing nano-particles is connected to the lattice of the calcium-containing core.
在一些實施方式中，含鈣核心包含氧化鈣、碳酸鈣或其組合。In some embodiments, the calcium-containing core comprises calcium oxide, calcium carbonate, or combinations thereof.
在一些實施方式中，含鋅奈米級粒子包含鋅、氧化鋅或其組合。In some embodiments, the zinc-containing nanoparticles comprise zinc, zinc oxide, or combinations thereof.
在一些實施方式中，含鋅牡蠣殼粉更包含脂肪酸類化合物分佈於含鈣核心的表面以及含鋅奈米級粒子的表面上。In some embodiments, the zinc-containing oyster shell powder further comprises fatty acid compounds distributed on the surface of the calcium-containing core and the surface of the zinc-containing nano-particles.
應當理解，前述的一般性描述和下文的詳細描述都是示例，並且旨在提供對所要求保護的本揭示內容的進一步解釋。It is to be understood that both the foregoing general description and the following detailed description are examples and are intended to provide further explanation of the disclosure as claimed.
可以理解的是，下述內容提供的不同實施方式或實施例可實施本揭露之標的不同特徵。特定構件與排列的實施例係用以簡化本揭露而非侷限本揭露。當然，這些僅是實施例，並且不旨在限制。舉例來說，以下所述之第一特徵形成於第二特徵上的敘述包含兩者直接接觸，或兩者之間隔有其他額外特徵而非直接接觸。此外，本揭露在複數個實施例中可重複參考數字及/或符號。這樣的重複是為了簡化和清楚，而並不代表所討論的各實施例及/或配置之間的關係。It can be understood that different implementations or examples provided in the following content can implement different features of the subject matter of the present disclosure. The examples of specific components and arrangements are used to simplify the present disclosure and not to limit the present disclosure. Of course, these are examples only and are not intended to be limiting. For example, the description below that a first feature is formed on a second feature includes that the two are in direct contact, or that there are other additional features between the two instead of direct contact. In addition, the present disclosure may repeat reference numerals and/or symbols in several embodiments. Such repetition is for simplicity and clarity and does not imply a relationship between the various embodiments and/or configurations discussed.
本說明書中所用之術語一般在本領域以及所使用之上下文中具有通常性的意義。本說明書中所使用的實施例，包括本文中所討論的任何術語的例子僅是說明性的，而不限制本揭示內容或任何示例性術語的範圍和意義。同樣地，本揭示內容不限於本說明書中所提供的一些實施方式。The terms used in this specification generally have their ordinary meanings in the art and the context in which they are used. The examples used in this specification, including examples of any term discussed herein, are illustrative only and do not limit the scope and meaning of the disclosure or any exemplified term. Likewise, the disclosure is not limited to some of the embodiments provided in this specification.
將理解的是，儘管本文可以使用術語第一、第二等來描述各種元件，但是這些元件不應受到這些術語的限制。這些術語用於區分一個元件和另一個元件。舉例來說，在不脫離本實施方式的範圍的情況下，第一元件可以被稱為第二元件，並且類似地，第二元件可以被稱為第一元件。It will be understood that, although the terms first, second etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of the present embodiments.
於本文中，術語「和/或」包含一個或複數個相關聯的所列項目的任何和所有組合。As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
於本文中，術語「包含」、「包括」、「具有」等應理解為開放式，即，意指包括但不限於。In this document, the terms "comprising", "including", "having" and the like should be interpreted as open-ended, that is, meaning including but not limited to.
於本文中，使用的「約」、「近似」、或「實質上」包括所述值和在本領域普通技術人員確定的特定值的可接受的偏差範圍內的平均值，考慮到所討論的測量和與測量相關的誤差的特定數量(即，測量系統的限制)。例如，「約」可以表示在所述值的一個或多個標準偏差內，或±30%、±20%、±10%、±5%內。再者，本文使用的「約」、「近似」、「相似」或「實質上」可依光學性質、蝕刻性質或其它性質，來選擇較可接受的偏差範圍或標準偏差，而可不用一個標準偏差適用全部性質。As used herein, use of "about," "approximately," or "substantially" includes stated values and averages within acceptable deviations from a particular value as determined by one of ordinary skill in the art, taking into account the The measurement and the specific amount of error associated with the measurement (ie, the limits of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±30%, ±20%, ±10%, ±5% of the stated value. Furthermore, the terms "about", "approximately", "similar" or "substantially" used herein may select a more acceptable range of deviation or standard deviation based on optical properties, etching properties or other properties, instead of using a standard Deviations apply to all properties.
如前所述，本發明提供製備含鋅牡蠣殼粉及其製備方法，相較習知的純牡蠣殼粉 (未經將含鋅添加物與牡蠣殼粉混合以及加熱生成氧化鋅的處理)，可提升抗菌效果以及抗菌耐水性 (經水洗後的抗菌性)。As mentioned above, the present invention provides the preparation of zinc-containing oyster shell powder and its preparation method. Compared with the conventional pure oyster shell powder (without mixing zinc-containing additives with oyster shell powder and heating to generate zinc oxide), It can improve antibacterial effect and antibacterial water resistance (antibacterial property after washing with water).
請參第1圖，本揭示內容的一些實施方式提供製備含鋅牡蠣殼粉的方法100，包含：步驟S110，提供牡犡殼粉；步驟S120，提供含鋅添加物；步驟S130，混合牡蠣殼粉與含鋅添加物，獲得混合物；以及步驟S140，加熱混合物，使混合物反應生成包含氧化鋅的含鋅牡蠣殼粉。Please refer to FIG. 1 , some embodiments of the disclosure provide a
首先，步驟S110，提供牡犡殼粉。在一些實施方式中，牡犡殼粉可由單殼貝外殼及/或雙殼貝外殼研磨而得，主要成分為碳酸鈣即可，其種類並無特別限制。在一些實施方式中，單殼貝外殼及/或雙殼貝外殼為牡蠣目牡蠣總科的雙殼綱軟體動物的外殼，例如但不限於牡蠣、文蛤、蜆、九孔、孔雀蛤、帆貝、鮑魚、珍珠貝、蝶貝、扇貝及上述之任意組合。此外，上述雙殼綱軟體動物的外殼一般含有重量百分比至少為90%的碳酸鈣，以及其他不可分離的成分 (例如氧化鈣、微量重金屬、或幾丁質以及蛋白質等有機物)。First, in step S110, provide the husk shell powder. In some embodiments, the shell powder of mite can be obtained by grinding the shells of monovalve shells and/or shells of bivalve shells, and the main component is only calcium carbonate, and its type is not particularly limited. In some embodiments, the shell of the monovalve and/or the shell of the bivalve is the shell of a bivalve mollusk of the order Oysteraceae Oysteroidea, such as but not limited to oysters, meretrix meretrix, clams, chrysalis, peacock clams, scallops , abalone, pearl oyster, butterfly shell, scallop and any combination of the above. In addition, the shells of the above-mentioned bivalve molluscs generally contain at least 90% by weight of calcium carbonate, and other inseparable components (such as calcium oxide, trace amounts of heavy metals, or organic substances such as chitin and protein).
在一些實施方式中，牡蠣殼粉的粒徑為50微米以下，例如1微米、10微米、20微米、30微米、40微米、50微米或前述任意區間的數值。在一實施方式中，牡犡殼粉的平均粒徑為亞微米級至微米級，例如10微米以下，舉例而言2微米至6微米 (2微米、3微米、4微米、5微米、6微米或前述任意區間的數值)。In some embodiments, the particle size of the oyster shell powder is less than 50 microns, such as 1 micron, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns or a value within any range of the foregoing. In one embodiment, the average particle size of the peony shell powder is submicron to micron, for example below 10 microns, for example 2 microns to 6 microns (2 microns, 3 microns, 4 microns, 5 microns, 6 microns or a value in any of the aforementioned intervals).
在一些實施方式中，可以在研磨前，將牡犡殼片先經800°C至1300°C的煅燒處理，將主要成分由碳酸鈣轉化為氧化鈣，再將牡犡殼片研磨，獲得牡犡殼粉，其中氧化鈣釋放用於抑菌的含氧自由基，可提升抗菌效果。在一實施方式中，牡犡殼粉依序經由以下步驟所獲得：提供牡犡殼；清水洗清牡犡殼以及刷除牡犡殼表面附著物，牡犡殼中碳酸鈣的重量百分比至少為90%(例如90%、91%、92%、93%、94%、95%、96%、97%、98%、99%、100%或前述任意區間的數值)；以300°C至500°C的溫度初步煅燒牡犡殼，去除有機物；初步粉碎牡犡殼為牡犡殼片；以800°C至1300°C的溫度 (例如800°C、850°C、900°C、950°C、1000°C、1050°C、1100°C、1150°C、1200°C、1250°C、1300°C、或前述任意區間的數值) 煅燒牡犡殼片，將碳酸鈣反應為氧化鈣；研磨分級牡犡殼片，獲得亞微米級至微米級的牡犡殼粉，牡犡殼粉中氧化鈣的重量百分比至少為90%(例如90%、91%、92%、93%、94%、95%、96%、97%、98%、99%、100%或前述任意區間的數值)。在一些其他實施方式中，可以在以800°C至1300°C的溫度煅燒牡蠣殼片前，對於牡蠣殼片進行鹼包覆處理、碳化處理或其組合，從而獲得具有氧化鈣核殼結構 (奈米級氧化鈣粒子分佈於微米級獲亞微米級的氧化鈣核心層表面) 的牡犡殼粉。舉例而言，可以經由對牡蠣殼片執行鹼包覆處理，獲得具有連續殼層的牡犡殼粉 (奈米級氧化鈣粒子與氧化鈣核心層相連)；或是對於牡蠣殼片執行鹼包覆處理以及碳化處理，獲得具有不連續殼層的牡犡殼粉 (奈米級氧化鈣粒子與氧化鈣核心層不相連)。值得一提的是，經過鹼包覆步驟或是鹼包覆步驟以及碳化步驟處理後，所形成的具有殼層結構的牡蠣殼粉，不僅提升白度 (表示物質表面白色的程度，可用粉體白度計測定而得) 及抗菌率 (降低細菌含量的百分比)，並且重金屬含量降低。In some embodiments, before grinding, the peony shell slices can be calcined at 800°C to 1300°C to convert the main component from calcium carbonate to calcium oxide, and then grind the peony shell slices to obtain peony X shell powder, in which calcium oxide releases oxygen-containing free radicals for antibacterial, which can enhance the antibacterial effect. In one embodiment, the husk powder is obtained through the following steps in sequence: providing husks; washing the husks with clear water and brushing off the surface attachments of the husks, and the weight percentage of calcium carbonate in the husks is at least 90% (such as 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100% or the value of any interval above); at 300°C to 500°C The temperature of ° C preliminarily calcines the peony shell to remove organic matter; the preliminary pulverization of the peony shell is the peony shell sheet; C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, or the value in any range of the foregoing) Calcining the oyster shell slices to react calcium carbonate into calcium oxide Grinding and classifying the husk slices to obtain the husk powder from submicron to micron, the percentage by weight of calcium oxide in the husk powder is at least 90% (such as 90%, 91%, 92%, 93%, 94% %, 95%, 96%, 97%, 98%, 99%, 100% or any value in the preceding range). In some other embodiments, before the oyster shell is calcined at a temperature of 800°C to 1300°C, the oyster shell is subjected to alkali coating treatment, carbonization treatment or a combination thereof, so as to obtain a calcium oxide core-shell structure ( Nano-scale calcium oxide particles are distributed on the surface of the calcium oxide core layer of micron or sub-micron scale) of oyster shell powder. For example, oyster shell powder can be obtained by performing an alkali coating process on oyster shell pieces to obtain oyster shell powder with a continuous shell layer (nanoscale calcium oxide particles are connected to the calcium oxide core layer); or performing alkali coating on oyster shell pieces Covering treatment and carbonization treatment, the oyster shell powder with discontinuous shell layer (nano-scale calcium oxide particles are not connected to the calcium oxide core layer) is obtained. It is worth mentioning that after the alkali coating step or the alkali coating step and the carbonization step, the formed oyster shell powder with a shell structure not only improves the whiteness (indicating the degree of whiteness of the material surface, but can also be used as a powder Whiteness meter) and antibacterial rate (percentage of reduced bacterial content), and heavy metal content decreased.
接著，請見步驟S120，提供含鋅添加物。在一些實施方式中，含鋅添加物包含含鋅有機物、含鋅無機物或其組合。在一些實施方式中，含鋅有機物包含硬脂酸鋅 (C 36H 70O 4Zn)、鈣鋅安定劑或其組合；含鋅無機物包含氯化鋅(ZnCl 2)、氫氧化鋅(Zn(OH) 2)、碳酸鋅(ZnCO 3)、鹼式碳酸鋅(ZnCO 3·2Zn(OH) 2·H 2O)或其組合。在一實施方式中，含鋅添加物採用碳酸鋅(ZnCO 3)或鹼式碳酸鋅(ZnCO 3·2Zn(OH) 2·H 2O)，不僅可以避免氯化鋅以及氫氧化氫的易於受潮團聚，反應不均的問題，也可避免硬脂酸鋅的反應過程冒黑煙的安全問題以及汙染問題。此外，相對於含鋅有機物 (單位重量中含鋅量較低)，含鋅添加物採用鹼式碳酸鋅以及碳酸鋅，則僅需添加較少量，便可獲得較高鋅含量的含鋅牡蠣殼粉。 Next, see step S120 , providing zinc-containing additives. In some embodiments, the zinc-containing additive comprises a zinc-containing organic, a zinc-containing inorganic, or a combination thereof. In some embodiments, the zinc-containing organic matter comprises zinc stearate (C 36 H 70 O 4 Zn ), calcium zinc stabilizer or a combination thereof; the zinc-containing inorganic matter comprises zinc chloride (ZnCl 2 ), zinc hydroxide (Zn( OH) 2 ), zinc carbonate (ZnCO 3 ), basic zinc carbonate (ZnCO 3 ·2Zn(OH) 2 ·H 2 O), or combinations thereof. In one embodiment, zinc carbonate (ZnCO 3 ) or basic zinc carbonate (ZnCO 3 ·2Zn(OH) 2 ·H 2 O) is used as the zinc-containing additive, which can not only avoid the easy moisture of zinc chloride and hydrogen hydroxide Agglomeration, the problem of inhomogeneous reaction, also can avoid the safety problem and the pollution problem that black smoke is emitted in the reaction process of zinc stearate. In addition, compared with zinc-containing organic matter (lower zinc content per unit weight), zinc-containing additives use basic zinc carbonate and zinc carbonate, and only a small amount can be added to obtain zinc-containing oysters with higher zinc content. shell powder.
接著，請見步驟S130，混合牡蠣殼粉與含鋅添加物，獲得混合物。在一些實施方式中，混合牡蠣殼粉與含鋅添加物的步驟為乾式固態混合 (即，僅將固態的反應物進行混合，不摻雜液態溶劑)。值得強調的是，相較於習知的濕式溶劑法(氧化鋅合成於液態溶劑中，例如使用醇類(甲醇或乙醇)為溶劑，與含鋅前驅物進行離子反應，合成氧化鋅、氫氧化鋅或是碳酸鋅，後續再經熱處理將溶劑、水或二氧化碳去除)，乾式固態混合不僅避免廢液排放的環保問題，並且可省略因溶劑處理而衍申的去除溶劑、加壓過濾、乾燥、粒徑分級等步驟，簡化製備流程。Next, see step S130, mixing oyster shell powder and zinc-containing additives to obtain a mixture. In some embodiments, the step of mixing the oyster shell meal and the zinc-containing additive is dry solid state mixing (ie, only solid reactants are mixed without doping with a liquid solvent). It is worth emphasizing that, compared with the conventional wet solvent method (zinc oxide is synthesized in a liquid solvent, for example, alcohols (methanol or ethanol) are used as solvents, and ion reactions are carried out with zinc-containing precursors to synthesize zinc oxide, hydrogen Zinc oxide or zinc carbonate, followed by heat treatment to remove solvent, water or carbon dioxide), dry solid-state mixing not only avoids the environmental protection problems of waste liquid discharge, but also can omit solvent removal, pressure filtration, and drying derived from solvent treatment , particle size classification and other steps to simplify the preparation process.
在一些實施方式中，含鋅添加物與牡蠣殼粉的重量份配比為0.05至1，例如0.05、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、或前述任意區間的數值。由於隨著重量份配比提升，可以提升含鋅牡蠣殼粉中的鋅含量，但成本也將隨之增加。在一實施方式中，重量份配比可以為0.25至1，以控制成本於合適的範圍中，同時含鋅牡蠣殼粉中具有合適的鋅含量。In some embodiments, the weight ratio of the zinc-containing additive to the oyster shell powder is 0.05 to 1, such as 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, or any of the foregoing The numeric value of the interval. Since the zinc content in the zinc-containing oyster shell powder can be increased along with the increase of the proportion by weight, the cost will also increase thereupon. In one embodiment, the weight ratio can be 0.25 to 1, so as to control the cost in an appropriate range, and at the same time, the zinc-containing oyster shell powder has an appropriate zinc content.
在一些實施方式中，混合牡蠣殼粉與含鋅添加物的溫度範圍為20°C至110°C，例如20°C、30°C、40°C、50°C、60°C、70°C、80°C、90°C、100°C、110°C、或前述任意區間的數值。在一些實施方式中，混合牡蠣殼粉與含鋅添加物的轉速範圍為150rpm至900 rpm (例如100 rpm、150 rpm、200 rpm、250 rpm、300 rpm、350 rpm、400 rpm、450 rpm、500 rpm、550 rpm、600 rpm、650 rpm、700 rpm、750 rpm、800 rpm、850 rpm、900 rpm、或前述任意區間的數值)，其中rpm為每分鐘轉速 revolution(s) per minute) 的縮寫)。在一些實施方式中，混合牡蠣殼粉與含鋅添加物的混合時間範圍為15分鐘至90分鐘 (例如15分鐘、30分鐘、45分鐘、60分鐘、75分鐘、90分鐘、或前述任意區間的數值)，以達到含鋅添加物披覆於牡蠣殼粉表面的狀態。可以了解的是，在前述混合條件中，隨著溫度、時間、或轉速的提升，混合效率隨之提升。In some embodiments, the temperature range of mixing oyster shell powder and zinc-containing additive is from 20°C to 110°C, such as 20°C, 30°C, 40°C, 50°C, 60°C, 70°C C, 80°C, 90°C, 100°C, 110°C, or a value within any of the aforementioned intervals. In some embodiments, the rotational speed range of mixing oyster shell meal and zinc-containing additive is 150rpm to 900rpm (such as 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm rpm, 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm, 800 rpm, 850 rpm, 900 rpm, or a value in any of the aforementioned intervals), where rpm is an abbreviation for revolution(s) per minute) . In some embodiments, the mixing time of mixing the oyster shell powder and the zinc-containing additive ranges from 15 minutes to 90 minutes (for example, 15 minutes, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, or any interval between the foregoing Numerical value), in order to achieve the state that zinc-containing additives are coated on the surface of oyster shell powder. It can be understood that, in the aforementioned mixing conditions, as the temperature, time, or rotational speed increase, the mixing efficiency increases accordingly.
接著，請見步驟S140，加熱混合物，使混合物反應生成包含氧化鋅的含鋅牡蠣殼粉。在一些實施方式中，加熱混合物的步驟，包含在150°C至1100°C (例如150°C、200°C、250°C、300°C、350°C、400°C、450°C、500°C、550°C、600°C、650°C、700°C、750°C、800°C、850°C、900°C、950°C、1000°C、1050°C、1100°C、或前述任意區間的數值)加熱混合物，其中若含鋅添加物採用硬脂酸鋅、鈣鋅安定劑、氯化鋅、鹼式碳酸鋅或是碳酸鋅，600°C為可生成氧化鋅的最低加熱溫度；若含鋅添加採用氫氧化鋅，200°C為可生成氧化鋅的最低加熱溫度。在一些實施方式中，加熱混合物的步驟，包含加熱混合物至預定時間，使含鋅牡蠣殼粉中的氧化鋅呈奈米級分佈 (粒徑小於1微米)，而不會團聚為微米級 (粒徑大於1微米)以上。在一些實施方式中，加熱混合物1小時至8小時 (例如1小時、2小時、3小時、4小時、5小時、6小時、7小時、8小時、或前述任意區間的數值)，其中4小時為將含鋅添加物完全轉化為氧化鋅 (或還原態鋅) 的最低加熱時間，不過隨著時間拉長 (例如大於8小時)，成長出的氧化鋅會發生團聚 (微米級以上的聚集) 的狀況，由於團聚造成氧化鋅的比表面積減少，降低抗菌效果。由於隨著加熱時間或溫度提升，含鋅牡蠣殼粉逐漸由白色漸趨灰黃色，色相較差，因此，在一實施方式中，加熱溫度設定為600°C以及加熱時間為4小時，可以在完全轉化含鋅添加物為氧化鋅 (或還原態鋅) 的前提下，獲得色相最好 (偏向白色) 的含鋅牡蠣殼粉。Next, please refer to step S140, heating the mixture to make the mixture react to generate zinc-containing oyster shell powder containing zinc oxide. In some embodiments, the step of heating the mixture comprises heating the mixture at 150°C to 1100°C (e.g., 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C C, or the value in any of the aforementioned intervals) heating the mixture, wherein if the zinc-containing additive adopts zinc stearate, calcium zinc stabilizer, zinc chloride, basic zinc carbonate or zinc carbonate, zinc oxide can be generated at 600°C The lowest heating temperature; if zinc hydroxide is used for zinc addition, 200°C is the lowest heating temperature that can generate zinc oxide. In some embodiments, the step of heating the mixture comprises heating the mixture for a predetermined time such that the zinc oxide in the zinc-containing oyster shell powder is distributed in nanometer scale (particle size less than 1 micron) without agglomerating into micron scale (particle size). diameter greater than 1 micron). In some embodiments, the mixture is heated for 1 hour to 8 hours (e.g., 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or any of the preceding values), wherein 4 hours The minimum heating time for the complete conversion of zinc-containing additives into zinc oxide (or reduced zinc), but as the time elongates (for example, more than 8 hours), the grown zinc oxide will agglomerate (agglomeration above the micron level) In the case of zinc oxide, the specific surface area of zinc oxide is reduced due to agglomeration, which reduces the antibacterial effect. As the heating time or temperature increases, the zinc-containing oyster shell powder gradually turns from white to grayish yellow, and its hue is poor. Therefore, in one embodiment, the heating temperature is set to 600° C. and the heating time is 4 hours. On the premise of converting the zinc-containing additives into zinc oxide (or reduced zinc), the zinc-containing oyster shell powder with the best hue (towards white) was obtained.
可以了解的是，經由加熱含鋅添加物與牡蠣殼粉，成長含鋅奈米級粒子於牡蠣殼粉表面，相較於未經鋅處理的牡蠣殼粉，具有較好的抗菌效果。具體而言，含鋅牡蠣殼粉中的含鋅奈米級粒子 (例如鋅、氧化鋅或其組合) 具有抗菌效果，並且經由奈米級的分佈，相較於較大粒徑的粒子 (例如微米級或亞微米級)，具有較大的比表面積 (單位質量所具有的表面積)。因此，含鋅奈米級粒子與牡蠣殼粉可雙管齊下，賦與含鋅牡蠣殼粉更為優異的抗菌效果。It can be understood that by heating the zinc-containing additive and oyster shell powder, zinc-containing nano-particles grow on the surface of oyster shell powder, which has a better antibacterial effect than oyster shell powder without zinc treatment. Specifically, zinc-containing nanoscale particles (such as zinc, zinc oxide, or a combination thereof) in zinc-containing oyster shell powder have antibacterial effects, and via nanoscale distribution, compared with larger particle sizes (such as Micron or submicron), has a larger specific surface area (surface area per unit mass). Therefore, zinc-containing nano-particles and oyster shell powder can work together to endow the zinc-containing oyster shell powder with a more excellent antibacterial effect.
關於含鋅奈米級粒子的抗菌機轉，詳細而言，含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉利用氧化鋅的光催化效應，產生不穩定的孤對電子或自由基，孤對電子或自由基可氧化分解有機物質 (例如細菌的組成結構)，破壞細菌；另一方面，還原態鋅可穿透細胞膜滲入到細胞的內部，與細菌體內的蛋白質、核酸中存在的巰基 (-SH)、氨基 (-NH 2) 等含硫、氮的官能團反應，使蛋白質變性，進而使細胞中的合成酶 (蛋白質合成酶) 喪失活性，阻斷細菌的代謝，抑制細菌的繁殖。當原細菌死亡後，還原態鋅可以從菌體中游離出來，再與其它細菌接觸，重複前述抗菌流程。因此，含鋅牡蠣殼粉的抗菌效果具有持久性。 Regarding the antibacterial mechanism of zinc-containing nanoparticles, in detail, zinc-containing oyster shell powder and modified zinc-containing oyster shell powder use the photocatalytic effect of zinc oxide to generate unstable lone pairs of electrons or free radicals, lone pair Electrons or free radicals can oxidize and decompose organic substances (such as the composition and structure of bacteria) and destroy bacteria; on the other hand, reduced zinc can penetrate the cell membrane into the interior of the cell, and the sulfhydryl group (- SH), amino (-NH 2 ) and other sulfur- and nitrogen-containing functional groups react to denature proteins, thereby inactivating synthetases (protein synthases) in cells, blocking bacterial metabolism, and inhibiting bacterial reproduction. When the original bacteria die, the reduced zinc can be freed from the bacteria, and then contact with other bacteria to repeat the above antibacterial process. Therefore, the antibacterial effect of zinc-containing oyster shell powder is persistent.
此外，本案含鋅牡蠣殼粉還可改善牡蠣殼粉中氧化鈣遇水流失的問題 (氧化鋅難溶於水)，具有較好的抗菌耐水性。In addition, the zinc-containing oyster shell powder in this case can also improve the loss of calcium oxide in oyster shell powder when encountering water (zinc oxide is difficult to dissolve in water), and has good antibacterial and water resistance.
另一方面，本揭示內容利用牡蠣殼粉做為含鋅添加物成長含鋅奈米級粒子的長晶載體，使得含鋅奈米級粒子分散於牡蠣殼粉表面成長，相較於直接於溶劑中反應生成含鋅奈米級粒子，可改善含鋅奈米級粒子因交互作用力大 (奈米效應) 易於團聚的情形。On the other hand, this disclosure uses oyster shell powder as a zinc-containing additive to grow zinc-containing nano-sized particles as a long-crystal carrier, so that zinc-containing nano-particles are dispersed on the surface of oyster shell powder to grow, compared with directly adding a solvent The medium reaction produces zinc-containing nano-particles, which can improve the situation that zinc-containing nano-particles are easy to agglomerate due to the large interaction force (nano effect).
在一些實施方式中，在加熱混合物的步驟之後，更包含在高於脂肪酸類化合物的熔點的溫度範圍中混合含鋅牡蠣殼粉與脂肪酸類化合物，獲得改質含鋅牡蠣殼粉，經由脂肪酸改質含鋅牡蠣殼粉，以改善含鋅牡蠣殼粉與有機高分子的相容性。可以了解的是，混合溫度需超過脂肪酸類化合物的熔點，以達到較好的改質效果。在一些實施方式中，可以在50°C至100°C (例如50°C、60°C、70°C、80°C、90°C、100°C、或前述任意區間的數值) 的溫度範圍中混合含鋅牡蠣殼粉與脂肪酸類化合物，其中脂肪酸類化合物可以採用12碳至22碳的短鏈脂肪酸(例如12碳、14碳、15碳、16碳、17碳、18碳、19碳、20碳、21碳、22碳或前述任意區間中的數值)。一般而言，12碳至14碳的脂肪酸類化合物的處理溫度範圍為50°C至60°C，16碳至18碳的脂肪酸類化合物的處理溫度範圍為70°C至90°C，若採用市售短鏈脂肪酸類化合物 (12碳至18碳) 進行改質，處理溫度範圍可以設定為70°C至90°C，以獲得較好的改質效果。在一些實施方式中，將含鋅牡蠣殼粉與脂肪酸類化合物的重量總和以100%計，則脂肪酸類化合物的重量百分比為0.5%至5% (例如0.5%、1%、2%、3%、4%、5%、或前述區間中的數值)，隨著添加量的提升，含鋅牡蠣殼粉與有機高分子的相容性也隨之提升。在一些實施方式中，改質的混合作用時間為15分鐘至90分鐘 (例如15分鐘、30分鐘、45分鐘、60分鐘、75分鐘、90分鐘、或前述區間中的數值)。在一些實施方式中，可以採用與混合牡蠣殼粉與含鋅添加物的步驟中相同或相似的攪拌葉片以及轉速進行混合，以提升混合效率。在一實施方式中，可以混合含鋅牡蠣殼粉與重量百分比2%的硬脂酸 (18碳)，在90°C中處理30分鐘進行改質。In some embodiments, after the step of heating the mixture, further comprising mixing zinc-containing oyster shell powder with the fatty acid compound at a temperature range higher than the melting point of the fatty acid compound to obtain modified zinc-containing oyster shell powder, through fatty acid modification Zinc-containing oyster shell powder was used to improve the compatibility of zinc-containing oyster shell powder and organic polymers. It can be understood that the mixing temperature needs to exceed the melting point of the fatty acid compound in order to achieve a better modification effect. In some embodiments, it may be at a temperature of 50°C to 100°C (such as 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any value in the foregoing range) Mix zinc-containing oyster shell powder and fatty acid compounds in the range, wherein fatty acid compounds can adopt short-chain fatty acids with 12 carbons to 22 carbons (such as 12 carbons, 14 carbons, 15 carbons, 16 carbons, 17 carbons, 18 carbons, 19 carbons , 20 carbons, 21 carbons, 22 carbons or a value in any of the aforementioned ranges). Generally speaking, the treatment temperature range for fatty acid compounds with 12 carbons to 14 carbons is 50°C to 60°C, and the treatment temperature range for fatty acid compounds with 16 carbons to 18 carbons is 70°C to 90°C. Commercially available short-chain fatty acid compounds (12 carbons to 18 carbons) are used for modification, and the treatment temperature range can be set at 70°C to 90°C to obtain a better modification effect. In some embodiments, the weight sum of the zinc-containing oyster shell powder and the fatty acid compound is calculated as 100%, and the weight percentage of the fatty acid compound is 0.5% to 5% (such as 0.5%, 1%, 2%, 3% , 4%, 5%, or the value in the aforementioned range), with the increase of the added amount, the compatibility of zinc-containing oyster shell powder and organic polymers also increases. In some embodiments, the modification mixing action time is 15 minutes to 90 minutes (eg, 15 minutes, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, or a value in the aforementioned range). In some embodiments, the same or similar stirring blades and rotating speed as in the step of mixing the oyster shell powder and the zinc-containing additive can be used for mixing, so as to improve the mixing efficiency. In one embodiment, zinc-containing oyster shell powder can be mixed with 2% by weight stearic acid (18 carbons), and treated at 90°C for 30 minutes for modification.
值得強調的是，經由使用脂肪酸類化合物對含鋅牡蠣殼粉改質，使得含鋅牡蠣殼粉與有機高分子的相容性提升，因此在將含鋅牡蠣殼粉與塑料原料 (例如聚乙烯、聚丙烯、聚氯乙烯等) 混煉，製成塑料製品時，相較於含鋅牡蠣殼粉與塑料原料所製備而得的塑膠製品，不論是抗菌效果或是抗菌耐水性均進一步地得到提升。It is worth emphasizing that the compatibility of zinc-containing oyster shell powder with organic polymers is improved by using fatty acid compounds to modify zinc-containing oyster shell powder. , polypropylene, polyvinyl chloride, etc.) to make plastic products, compared with the plastic products prepared from zinc-containing oyster shell powder and plastic raw materials, both the antibacterial effect and antibacterial water resistance are further improved promote.
本揭示內容的一些實施方式中還提供含鋅牡蠣殼粉，包含含鈣核心以及複數含鋅奈米級粒子，其中含鋅奈米級粒子散佈於含鈣核心的表面，其中含鋅奈米級粒子的其中一者的晶格與含鈣核心的晶格相連 (例如可以經由X光繞射儀 (X-Ray Diffraction；XRD) 分析而得)。由於習知濕式溶劑法所獲得的氧化鋅晶格與氧化鈣晶格分離，因此，根據含鋅奈米級粒子的晶格與含鈣核心的晶格是否相連，可以判斷製程所採用的方法，是否為經由乾式固態混合再加熱，成長含鋅奈米級粒子的步驟。Some embodiments of the present disclosure also provide zinc-containing oyster shell powder, comprising a calcium-containing core and a plurality of zinc-containing nanoparticles, wherein the zinc-containing nanoparticles are dispersed on the surface of the calcium-containing core, wherein the zinc-containing nanoscale particles The lattice of one of the particles is connected to the lattice of the calcium-containing core (for example, it can be obtained by X-Ray Diffraction (XRD) analysis). Since the zinc oxide lattice obtained by the conventional wet solvent method is separated from the calcium oxide lattice, the method used in the process can be judged according to whether the lattice of the zinc-containing nanoscale particles is connected to the lattice of the calcium-containing core. , whether it is a step of growing zinc-containing nano-particles through dry solid-state mixing and reheating.
在一些實施方式中，含鈣核心包含氧化鈣、碳酸鈣或其組合，根據方法100中加熱溫度的差異，主要成分將有所不同，例如曾經以800°C以上的溫度加熱，則主要成分為氧化鈣 (碳酸鈣轉化而得)，若未達800°C的溫度加熱，則主要成分為碳酸鈣。在一些實施方式中，含鋅奈米級粒子包含鋅、氧化鋅或其組合。在一些其他實施方式中，含鋅牡蠣殼粉更包含脂肪酸類化合物分佈 (經由凡得瓦力) 於含鈣核心的表面以及含鋅奈米級粒子的表面上，例如脂肪酸類化合物的親水端朝向含鋅牡蠣殼粉，疏水端朝向外界。In some embodiments, the calcium-containing core comprises calcium oxide, calcium carbonate or a combination thereof, and the main composition will vary according to the difference in heating temperature in
在一些實施方式中，含鈣核心的粒徑與牡蠣殼粉相近，可以為亞微米級或微米級，例如50微米以下 (舉例而言2微米至6微米)。在一些實施方式中，含鋅奈米級粒子的粒徑為100奈米以下，例如30奈米至100奈米 (30奈米、40奈米、50奈米、60奈米、70奈米、80奈米、90奈米、100奈米或前述任意區間的數值)。In some embodiments, the particle size of the calcium-containing core is similar to that of oyster shell powder, which may be submicron or micron, such as below 50 microns (for example, 2 microns to 6 microns). In some embodiments, the particle size of the zinc-containing nanoparticles is less than 100 nm, such as 30 nm to 100 nm (30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nanometers, 90 nanometers, 100 nanometers, or a value in any range of the foregoing).
在一些實施方式中，可以將含鋅牡蠣殼粉 (或經改質含鋅牡蠣殼粉 (經脂肪酸改質))與塑料原料 (例如聚乙烯、聚丙烯、聚氯乙烯等)混煉，製備出相較於添加牡犡殼粉，抗菌效果以及抗菌耐水性提升的塑膠製品。In some embodiments, zinc-containing oyster shell powder (or modified zinc-containing oyster shell powder (modified by fatty acid)) can be mixed with plastic raw materials (such as polyethylene, polypropylene, polyvinyl chloride, etc.) to prepare Compared with the addition of oyster shell powder, plastic products have improved antibacterial effect and antibacterial water resistance.
以下提供含鋅牡蠣殼粉以及經脂肪酸改質的改質含鋅牡蠣殼粉的製備方法，以及以含鋅牡蠣殼以及改質含鋅牡蠣殼粉及其所製備而成之塑膠製品的性能分析的相關實施例，以具體說明本揭示內容之一些實施方式。The following provides the preparation method of zinc-containing oyster shell powder and modified zinc-containing oyster shell powder modified by fatty acid, as well as performance analysis of zinc-containing oyster shell and modified zinc-containing oyster shell powder and the plastic products prepared therefrom Related examples are provided to illustrate some implementations of the present disclosure.
一、含鋅牡蠣殼粉的製備1. Preparation of zinc-containing oyster shell powder
1.製備牡蠣殼粉1. Preparation of oyster shell powder
首先，提供牡蠣殼。接著，用清水將牡蠣殼洗清，刷除表面附著物(例如藻類和砂石)，在300°C至500°C的溫度中加熱處理燒除有機物(例如幾丁質、蛋白質)之後，初步粉碎成3毫米至5毫米的牡蠣殼片，牡蠣殼片主要成份(重量百分比大於90%) 為碳酸鈣(CaCO 3)。此外，牡蠣殼片還可包含少量的氧化鈣。接著，將牡蠣殼片以800°C至1300°C的溫度煅燒，將碳酸鈣反應成氧化鈣(CaO)，最後經過研磨分級，得到平均粒徑約為2微米至6微米，主要成分為氧化鈣的牡蠣殼粉。 First, oyster shells are offered. Next, wash the oyster shells with clean water, brush off surface attachments (such as algae and gravel), heat treatment at a temperature of 300°C to 500°C to burn off organic matter (such as chitin, protein), and initially Crushed into oyster shells of 3 mm to 5 mm, the main component (more than 90% by weight) of the oyster shells is calcium carbonate (CaCO 3 ). In addition, oyster shell flakes may also contain small amounts of calcium oxide. Next, the oyster shell slices are calcined at a temperature of 800°C to 1300°C, and the calcium carbonate is reacted into calcium oxide (CaO). Finally, after grinding and classification, the average particle size is about 2 microns to 6 microns, and the main component is oxide Calcium oyster shell powder.
在一些其他實施例中，亦可省略以800°C至1300°C的溫度煅燒牡蠣殼片的步驟，而直接將牡蠣殼片經研磨分級，獲得主要成分為碳酸鈣的牡蠣殼粉。In some other embodiments, the step of calcining the oyster shell slices at a temperature of 800°C to 1300°C may also be omitted, and the oyster shell slices are directly ground and classified to obtain oyster shell powder whose main component is calcium carbonate.
可以了解的是，相對於主要成分為碳酸鈣的牡蠣殼粉，主要成分為氧化鈣的牡蠣殼粉可釋放更多的含氧自由基，具備較好的抑菌率。It can be understood that compared with oyster shell powder whose main component is calcium carbonate, oyster shell powder whose main component is calcium oxide can release more oxygen-containing free radicals and has a better antibacterial rate.
2.混合牡蠣殼粉與含鋅添加物2. Mix oyster shell powder with zinc additive
首先，為最適化牡蠣殼粉與含鋅添加物的混合條件，執行攪拌條件初測試。First, a preliminary test of stirring conditions was performed to optimize the mixing conditions of oyster shell powder and zinc-containing additives.
攪拌條件初測試是將牡蠣殼粉與特定種類的含鋅添加物，經攪拌器 (例如請參第2A圖的攪拌葉片組裝示意圖，自下而上依序包含第2B圖中的攪拌葉片T1至T4的攪拌葉片組，購自僑隆機械有限公司，商品型號CL-F10) 以不同攪拌條件處理後，形成混合物，接著，進行煅燒。再以掃描式電子顯微鏡觀察含鋅添加物所轉化的含鋅奈米級粒子 (例如氧化鋅以及還原態鋅粒子，粒徑約為30奈米至100奈米) 於牡蠣殼粉表面的分散情況，從而判斷在不同的葉片轉速 (300rpm、600rpm)、不同的攪拌溫度 (室溫 (約25°C)、90°C)、以及不同的攪拌時間 (30分鐘、60分鐘)等攪拌條件中，牡蠣殼粉與含鋅添加物的混合效果。The initial test of stirring conditions is to mix oyster shell powder and specific zinc-containing additives through a stirrer (for example, please refer to the schematic diagram of the assembly of stirring blades in Figure 2A, which includes stirring blades T1 to T1 in Figure 2B from bottom to top). The T4 stirring blade set, purchased from Qiaolong Machinery Co., Ltd. (product model CL-F10) was treated with different stirring conditions to form a mixture, and then to be calcined. Scanning electron microscopy was used to observe the dispersion of zinc-containing nano-particles (such as zinc oxide and reduced zinc particles, with a particle size of about 30 nm to 100 nm) converted from zinc-containing additives on the surface of oyster shell powder , thus judging that in different stirring conditions such as blade speed (300rpm, 600rpm), different stirring temperatures (room temperature (about 25°C), 90°C), and different stirring times (30 minutes, 60 minutes), Mixing effect of oyster shell powder with zinc-containing additives.
攪拌初測試結果呈現，葉片轉速採用600rpm、攪拌溫度採用90°C、攪拌時間採用60分鐘時，相對於其他條件，可以使得成長出的含鋅奈米級粒子較好地分散於牡蠣殼粉表面(請參第3A圖，箭頭A1)。反觀其他攪拌條件，例如請參第3B圖 (攪拌條件與第3A圖大致上相近，與第3A圖的差異在於，攪拌溫度採用25°C)，含鋅添加物分散效果較為不佳，造成經加熱後，含鋅奈米級粒子較不容易成長於牡蠣殼粉表面，甚至有團聚 (箭頭A2，例如呈微米級聚集以上) 的狀況；並且，將第3B圖攪拌條件中的葉片轉速改採為300rpm時，也會呈現與第3B圖相近的結果，例如含鋅添加物分散效果較為不佳、甚至團聚的狀況。The results of the initial mixing test show that when the blade speed is 600rpm, the stirring temperature is 90°C, and the stirring time is 60 minutes, compared with other conditions, the grown zinc-containing nano-sized particles can be better dispersed on the surface of oyster shell powder (Please refer to Figure 3A, arrow A1). In contrast to other stirring conditions, for example, please refer to Figure 3B (stirring conditions are roughly similar to Figure 3A, the difference from Figure 3A is that the stirring temperature is 25°C), the dispersion effect of zinc-containing additives is relatively poor, resulting in After heating, zinc-containing nanoscale particles are less likely to grow on the surface of oyster shell powder, and even agglomerate (arrow A2, such as above micron-scale aggregation); and, change the blade speed in the stirring condition in Figure 3B to adopt When the speed is 300rpm, the results similar to those in Figure 3B will also appear, for example, the dispersion effect of zinc-containing additives is relatively poor, or even agglomerated.
經攪拌前測試確立最佳攪拌條件後，採用最佳攪拌條件，將牡蠣殼粉以及不同種類的含鋅添加物，搭配不同的混合配比 (例如使得含鋅添加物的重量百分比為5%至50%)，分別進行混合，獲得混合物 (具體混合配比可同參下述表1)。含鋅添加物的種類可包含：1. 含鋅有機物或2. 含鋅無機物。含鋅有機物例如硬脂酸鋅或鈣鋅安定劑，後續以硬脂酸鋅代表。含鋅無機物例如氯化鋅、氫氧化鋅、鹼式碳酸鋅、或碳酸鋅。After the test before stirring establishes the best stirring conditions, adopt the best stirring conditions to mix oyster shell powder and different types of zinc-containing additives with different mixing ratios (such as making the weight percentage of zinc-containing additives be 5% to 50%), mix respectively, obtain mixture (concrete mixing proportion can refer to following table 1 with reference). Types of zinc-containing additives may include: 1. zinc-containing organics or 2. zinc-containing inorganics. Zinc-containing organic substances such as zinc stearate or calcium-zinc stabilizers are subsequently represented by zinc stearate. Zinc-containing inorganic substances such as zinc chloride, zinc hydroxide, basic zinc carbonate, or zinc carbonate.
3. 加熱混合物 (牡蠣殼粉以及含鋅添加物)3. Heating the mixture (oyster shell powder with zinc addition)
加熱含有牡蠣殼粉以及含鋅添加物的混合物，使氧化鋅或還原態鋅成長於牡蠣殼粉表面，獲得含鋅牡蠣殼粉，並比較不同種類的含鋅添加物種類，在不同加熱溫度 (200°C、400°C、600°C、1000°C)以及加熱時間 (2小時、2.5小時、3小時、3.5小時、4小時)時，含鋅牡蠣殼粉的可生成條件、生成速度以及含鋅牡蠣殼粉的品質 (例如團聚情形以及色相)，從而確定較合適的煅燒條件。Heat the mixture containing oyster shell powder and zinc-containing additives, so that zinc oxide or reduced zinc grows on the surface of oyster shell powder to obtain zinc-containing oyster shell powder, and compare different types of zinc-containing additives, at different heating temperatures ( 200°C, 400°C, 600°C, 1000°C) and heating time (2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours), the production conditions, production speed and The quality of zinc-containing oyster shell powder (such as agglomeration and hue) determines the more suitable calcination conditions.
含鋅牡蠣殼粉的可生成條件方面，含鋅添加物為硬脂酸鋅、氯化鋅、鹼式碳酸鋅、碳酸鋅時，600°C以上可以生成氧化鋅；含鋅添加物為氫氧化鋅時，200°C以上即可以生成氧化鋅。In terms of the production conditions of zinc-containing oyster shell powder, when the zinc-containing additive is zinc stearate, zinc chloride, basic zinc carbonate, and zinc carbonate, zinc oxide can be generated above 600°C; the zinc-containing additive is hydroxide Zinc oxide can be formed above 200°C.
含鋅牡蠣殼粉的生成速度方面，加熱時間4小時以上，各組的含鋅添加物則可完全反應為氧化鋅 (或鋅)，若小於4小時，則含鋅添加物尚無法完全轉化為氧化鋅 (或鋅)。此外，在其他 (非前述列舉條件) 針對加熱時間的實施例中還觀察到，若加熱時間過長 (例如大於8小時)，則成長的氧化鋅會發生團聚的狀況。因此，設定加熱時間為4小時至8小時，可以使含鋅添加物完全反應，並且降低氧化鋅的團聚現象。In terms of the generation rate of zinc-containing oyster shell powder, if the heating time is more than 4 hours, the zinc-containing additives of each group can be completely reacted into zinc oxide (or zinc), and if it is less than 4 hours, the zinc-containing additives cannot be completely converted into Zinc oxide (or zinc). In addition, it was also observed in other examples (other than the conditions listed above) regarding the heating time that if the heating time is too long (for example greater than 8 hours), the grown zinc oxide will agglomerate. Therefore, setting the heating time to 4 hours to 8 hours can completely react the zinc-containing additive and reduce the agglomeration phenomenon of zinc oxide.
含鋅牡蠣殼粉色相方面，隨著加熱時間越長或是加熱溫度越高，含鋅牡蠣殼粉顏色將更趨灰黃色，色相越差，影響終端塑料製品外觀色相。As for the pink phase of zinc-containing oyster shell, the longer the heating time or the higher the heating temperature, the color of zinc-containing oyster shell powder will become more grayish-yellow, and the hue will be worse, which will affect the appearance and hue of the terminal plastic products.
因此，加熱溫度設定為600°C以及加熱時間為4小時，可以在完全轉化含鋅添加物為氧化鋅 (或還原態鋅) 的前提下，獲得色相最好的含鋅牡蠣殼粉。Therefore, if the heating temperature is set to 600°C and the heating time is 4 hours, the zinc-containing oyster shell powder with the best hue can be obtained under the premise of completely converting the zinc-containing additive into zinc oxide (or reduced zinc).
接著，採用加熱溫度設定為600°C以及加熱時間為4小時的加熱條件，在不同添加含量以及不同種類的含鋅添加物的條件中，加熱牡蠣殼粉與含鋅添加物，比對所生成的含鋅牡蠣殼粉的鋅含量以及加熱操作的安全性等面向的表現，其中各組含鋅牡蠣殼粉中的鋅含量請參表1。Next, using the heating conditions that the heating temperature is set to 600°C and the heating time is 4 hours, in the conditions of different additive contents and different types of zinc-containing additives, heating oyster shell powder and zinc-containing additives, and comparing the generated The zinc content of zinc-containing oyster shell powder and the safety of heating operation, etc., for the zinc content of each group of zinc-containing oyster shell powder, please refer to Table 1.
表1、含鋅添加物種類及其重量百分比與含鋅牡蠣殼粉中的鋅含量關係表 (*請參註解)
註1：表1中的鋅含量採用電感耦合電漿體原子發射光譜法 (Inductively coupled plasma atomic emission spectroscopy；ICP-AES) 所測定而得。Note 1: The zinc content in Table 1 was determined by Inductively coupled plasma atomic emission spectroscopy (ICP-AES).
註2：由於氯化鋅為酸性和氫氧化氫為鹼性，性質上容易受潮，攪拌時受潮粉體與牡蠣殼粉難均勻分散，進而造成偏析，導致含鋅牡蠣殼粉的鋅含量極低，偏離設定值，並且粉體的酸鹼性以及受潮粉體易對設備造成損傷，後續討論主要針對硬脂酸鋅、鹼式碳酸鋅以及碳酸鋅。Note 2: Since zinc chloride is acidic and hydrogen hydroxide is alkaline, it is easy to be damp in nature, and it is difficult to disperse the wet powder and oyster shell powder evenly during stirring, which will cause segregation, resulting in extremely low zinc content in zinc-containing oyster shell powder , deviate from the set value, and the acidity and alkalinity of the powder and the wet powder are easy to cause damage to the equipment. The follow-up discussion mainly focuses on zinc stearate, basic zinc carbonate and zinc carbonate.
表1結果呈現，相對於鹼式碳酸鋅以及碳酸鋅 (含鋅無機物)，硬脂酸鋅 (含鋅有機物) 因含短碳鏈，分子量大，在單位重量中含鋅量較低，因此，需要較高的添加量，方可達到與含鋅無機物組別相近的鋅含量。舉例而言，當硬脂酸鋅的重量份配比0.25，鋅含量僅為21,613ppm，碳酸鋅的重量份配比0.2 (小於硬脂酸鋅的重量份配比0.25)，鋅含量即可達29,032 ppm (大於硬脂酸鋅的鋅含量)；或是當硬脂酸鋅的重量份配比0.5，鋅含量僅為49,108ppm，碳酸鋅的重量份配比0.225 (小於硬脂酸鋅的重量份配比0.5)，鋅含量即可達152,454ppm (高於硬脂酸鋅的鋅含量)。Table 1 result presents, with respect to basic zinc carbonate and zinc carbonate (zinc-containing inorganic matter), zinc stearate (zinc-containing organic matter) is because of containing short carbon chain, molecular weight is big, and zinc content in unit weight is lower, therefore, A higher amount of addition is required to achieve a zinc content similar to that of the zinc-containing inorganic group. For example, when the weight ratio of zinc stearate is 0.25, the zinc content is only 21,613ppm, and the weight ratio of zinc carbonate is 0.2 (less than the weight ratio of zinc stearate 0.25), the zinc content can reach 29,032 ppm (greater than the zinc content of zinc stearate); or when the weight ratio of zinc stearate is 0.5, the zinc content is only 49,108ppm, and the weight ratio of zinc carbonate is 0.225 (less than the weight of zinc stearate Part ratio 0.5), the zinc content can reach 152,454ppm (higher than zinc stearate zinc content).
此外，加熱操作的安全性方面，硬脂酸鋅於高溫煅燒時會產生黑煙，黑煙不僅影響操作視線，還可能對身體存在危害，存在安全風險。In addition, in terms of the safety of heating operation, zinc stearate will produce black smoke when calcined at high temperature. The black smoke not only affects the sight of the operation, but may also be harmful to the body and pose a safety risk.
相對而言，鹼式碳酸鋅以及碳酸鋅並無氯化鋅以及氫氧化氫的易於受潮問題，也不存在硬脂酸鋅反應過程冒黑煙的安全以及汙染問題，使用上較為方便以及安全。此外，相對於含鋅有機物，鹼式碳酸鋅以及碳酸鋅僅需添加少量，即可獲得更高的成品鋅含量。Relatively speaking, basic zinc carbonate and zinc carbonate do not have the moisture-prone problem of zinc chloride and hydrogen hydroxide, and do not have the safety and pollution problems of black smoke during the zinc stearate reaction process, and are more convenient and safe to use. In addition, compared with zinc-containing organic substances, only a small amount of basic zinc carbonate and zinc carbonate can be added to obtain a higher zinc content in the finished product.
4. 脂肪酸類化合物改質含鋅牡蠣殼粉4. Modification of zinc-containing oyster shell powder by fatty acid compounds
由於含鋅牡蠣殼粉為無機物，與有機高分子 (例如塑料) 的相容性存在限制。為改善含鋅牡蠣殼粉與有機高分子的相容性，混合含鋅牡蠣殼粉與短鏈脂肪酸 (例如當含鋅牡蠣殼粉與短鏈脂肪酸的重量總和設定為100%時，若選用硬脂酸，硬脂酸的重量百分比可以為0.5%、1.0%、1.5%、或2.0%)，在90°C中處理30分鐘，對於含鋅牡蠣殼粉進行改質，獲得改質含鋅牡蠣殼粉。可以了解的是，亦可以其他脂肪酸類化合物取代硬脂酸，本揭示內容並不以此為限。Due to the inorganic nature of zinc-containing oyster shell powder, there are limitations in compatibility with organic polymers such as plastics. In order to improve the compatibility of zinc-containing oyster shell powder and organic polymers, mix zinc-containing oyster shell powder and short-chain fatty acids (for example, when the weight sum of zinc-containing oyster shell powder and short-chain fatty acids is set to 100%, if hard Fatty acid, the percentage by weight of stearic acid can be 0.5%, 1.0%, 1.5%, or 2.0%), handle 30 minutes in 90 ℃, carry out modification for zinc-containing oyster shell powder, obtain the modified zinc-containing oyster shell powder. It can be understood that stearic acid can also be replaced by other fatty acid compounds, and the disclosure is not limited thereto.
需要特別注意的是，使用脂肪酸改質含鋅牡蠣殼粉，處理溫度需超過脂肪酸的熔點，以使得脂肪酸可以經由凡得瓦力均勻分佈於含鋅牡蠣殼粉的表面 (例如親水端朝向含鋅牡蠣殼粉)。Special attention should be paid to the use of fatty acid to modify zinc-containing oyster shell powder, the treatment temperature must exceed the melting point of the fatty acid, so that the fatty acid can be evenly distributed on the surface of the zinc-containing oyster shell powder through van der Waals force (for example, the hydrophilic end faces the zinc-containing oyster shell powder).
可以了解的是，脂肪酸類化合物添加的重量百分比可以隨著含鋅牡蠣殼粉的比表面積調整，即，對應粒徑大小調整，使得改質含鋅牡蠣殼粉達到更好的改質效果以及與有機高分子的相容性。例如含鋅牡蠣殼粉的粒徑越小 (比表面積越大)，則脂肪酸類化合物所添加的重量百分比越高。It can be understood that the weight percentage of the fatty acid compound can be adjusted with the specific surface area of the zinc-containing oyster shell powder, that is, the corresponding particle size adjustment, so that the modified zinc-containing oyster shell powder can achieve a better modification effect and be compatible with the zinc-containing oyster shell powder. Compatibility of organic polymers. For example, the smaller the particle size (the larger the specific surface area) of the zinc-containing oyster shell powder, the higher the weight percentage of the fatty acid compound added.
二、含鋅牡蠣殼粉的性能分析2. Performance analysis of zinc-containing oyster shell powder
1. 鑑定含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉1. Identification of zinc-containing oyster shell powder and modified zinc-containing oyster shell powder
1.1.電子顯微鏡1.1. Electron microscope
將牡蠣殼粉、含鋅牡蠣殼粉、改質含鋅牡蠣殼粉分別放置於碳膠帶，鍍上白金(鉑)，使用掃描式電子顯微鏡進行拍攝作業，拍攝照片請參第4圖 (牡蠣殼粉，放大倍率為4萬倍) 以及第5A圖至第5B圖 (在4萬倍放大倍率下，不同視角下的改質含鋅牡蠣殼粉)，由於含鋅牡蠣殼粉的電子顯微鏡影像與改質含鋅牡蠣殼粉大體上相似，因此此處以改質含鋅牡蠣殼粉的結果代表呈現(註：電子顯微鏡中無法觀察到脂肪酸類化合物)。Place oyster shell powder, zinc-containing oyster shell powder, and modified zinc-containing oyster shell powder on carbon tapes respectively, plate platinum (platinum), and use a scanning electron microscope to take pictures. For photos, please refer to Figure 4 (oyster shell powder, 40,000 times magnification) and Figures 5A to 5B (at 40,000 times magnification, modified zinc-containing oyster shell powder at different viewing angles), due to the electron microscope images of zinc-containing oyster shell powder and The modified zinc-containing oyster shell powder is generally similar, so the results of the modified zinc-containing oyster shell powder are presented here as a representative (note: fatty acid compounds cannot be observed in the electron microscope).
電子顯微鏡影像呈現，相較於第4圖的牡蠣殼粉，第5A圖至第5B圖的改質含鋅牡蠣殼粉中還包含複數含鋅奈米級粒子Z0散佈於含鈣核心C0 (原牡蠣殼粉) 的表面，其中含鈣核心C0的粒徑為亞微米級或微米級。Electron microscope images show that, compared to the oyster shell powder in Figure 4, the modified zinc-containing oyster shell powder in Figures 5A to 5B also contains a plurality of zinc-containing nano-sized particles Z0 scattered in the calcium-containing core C0 (originally oyster shell powder), wherein the particle size of the calcium-containing core CO is submicron or micron.
1.2.X光繞射儀 (X-Ray Diffraction；XRD)1.2. X-Ray Diffraction (X-Ray Diffraction; XRD)
將含鋅牡蠣殼粉或改質含鋅牡蠣殼粉塗抹於XRD專用載台，將載台置入XRD腔體進行分析。XRD可以根據X光對於粉體的繞射產生圖譜，並從圖譜資料庫比對，推論出粉體中的排列結構以及無機晶體的成份，結果請見第6圖。由於含鋅牡蠣殼粉的分析結果與改質含鋅牡蠣殼粉大體上相似，因此此處以改質含鋅牡蠣殼粉的結果代表呈現。Apply zinc-containing oyster shell powder or modified zinc-containing oyster shell powder to the special XRD stage, and put the stage into the XRD chamber for analysis. XRD can generate a spectrum based on the X-ray diffraction of the powder, and compare it with the spectrum database to infer the arrangement structure in the powder and the composition of the inorganic crystal. Please see Figure 6 for the results. Since the analysis results of zinc-containing oyster shell powder are generally similar to those of modified zinc-containing oyster shell powder, the results of modified zinc-containing oyster shell powder are presented here as a representative.
第6圖中，可以觀察到改質含鋅牡蠣殼粉中包含氧化鈣 (CaO) 晶體、碳酸鈣 (CaCO 3) 晶體以及氧化鋅 (ZnO) 晶體。並且值得注意的是，習知濕式溶劑法所製備而得的粉體中，氧化鋅晶格與氧化鈣晶格分離。然而，本揭示內容以乾式固態混合的方式製備改質含鋅牡蠣殼粉，改質含鋅牡蠣殼粉中部分的氧化鋅晶格與氧化鈣晶格相連，例如請見箭頭A3 (含鋅牡蠣殼粉結果亦同)。具體而言，箭頭A3處可見兩相鄰波峰具有一凹入點P相連。此外，需說明的是，儘管第6圖未特別例示，但改質含鋅牡蠣殼粉以及含鋅牡蠣殼粉中亦存在還原態鋅晶體。 In Figure 6, it can be observed that the modified zinc-containing oyster shell powder contains calcium oxide (CaO) crystals, calcium carbonate (CaCO 3 ) crystals and zinc oxide (ZnO) crystals. And it is worth noting that in the powder prepared by the conventional wet solvent method, the zinc oxide lattice is separated from the calcium oxide lattice. However, the disclosure prepares modified zinc-containing oyster shell powder in a dry solid-state mixing manner, and part of the zinc oxide lattice in the modified zinc-containing oyster shell powder is connected with the calcium oxide lattice, for example, see arrow A3 (zinc-containing oyster shell powder Shell powder results are the same). Specifically, it can be seen at the arrow A3 that two adjacent peaks are connected by a concave point P. In addition, it should be noted that, although not specifically illustrated in FIG. 6 , reduced zinc crystals also exist in the modified zinc-containing oyster shell powder and the zinc-containing oyster shell powder.
2.含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉的抗菌效果2. Antibacterial effect of zinc-containing oyster shell powder and modified zinc-containing oyster shell powder
2.1試片抗菌率測試2.1 Antibacterial rate test of test piece
為測試第一部份實施例所製備而得的粉體，應用於塑膠製品的抗菌率，將不同重量百分比的牡蠣殼粉、實施例第一部份所獲得的含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉 (經重量百分比為2%的硬脂酸改質，表示在混合含鋅牡蠣殼粉與硬脂酸，以進行改質的步驟中，若含鋅牡蠣殼粉與硬脂酸的重量總和設定為100%，硬脂酸所添加的重量百分比為2%) 各組粉體分別以重量百分比0%至3% (將粉體與線性低密度聚乙烯的總和設定為100%) 添加至線性低密度聚乙烯 (Linear low-density polyethylene；LLDPE) 的基材中，製備為5公分x5公分的試片。接著，根據日本產業標準JIS Z 2801的抗菌測試流程，以大腸桿菌為測試菌株，比較牡蠣殼粉、含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉組別以及添加不同粉體含量的試片的抗菌率，結果請見下表2。In order to test the antibacterial rate of the powder prepared in the first part of the embodiment and applied to plastic products, different weight percentages of oyster shell powder, zinc-containing oyster shell powder obtained in the first part of the embodiment and modified Zinc-containing oyster shell powder (modified by 2% stearic acid by weight means that in the step of mixing zinc-containing oyster shell powder and stearic acid, if the zinc-containing oyster shell powder and stearic acid The sum of the weights of the stearic acid is set as 100%, and the weight percentage added by stearic acid is 2%). Added to a linear low-density polyethylene (Linear low-density polyethylene; LLDPE) substrate to prepare a 5 cm x 5 cm test piece. Then, according to the antibacterial test process of Japanese industrial standard JIS Z 2801, Escherichia coli was used as the test strain to compare oyster shell powder, zinc-containing oyster shell powder, modified zinc-containing oyster shell powder groups, and test pieces with different powder contents The antibacterial rate, the results are shown in Table 2 below.
具體而言，日本產業標準JIS Z 2801的抗菌測試流程包含 (各條件均以三片試片測試)：(1) 以75%酒精清洗試片 (2) 接種大腸桿菌菌液於試片上 (3) 蓋上覆膜於試片上，固定菌液 (4) 25°C的溫度中培養24小時 (5) 以10毫升培養液 (不含細菌) 沖洗試片 (6) 再培養試片24小時，計算各組的抗菌率，其中，以不添加任何粉體的試片做為抗菌率為0%的換算標準。Specifically, the antibacterial test procedure of the Japanese Industrial Standard JIS Z 2801 includes (all conditions are tested with three test pieces): (1) Clean the test piece with 75% alcohol (2) Inoculate the E. coli bacteria solution on the test piece (3 ) Cover the test piece with a film, fix the bacteria solution (4) incubate at a temperature of 25°C for 24 hours (5) rinse the test piece with 10 ml of culture solution (without bacteria) (6) incubate the test piece for another 24 hours, Calculate the antibacterial rate of each group, wherein, the test piece without adding any powder is used as the conversion standard of 0% antibacterial rate.
表2、牡蠣殼粉、含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉的抗菌率比較表
根據表2，可以觀察到各組試片中，隨著粉體的重量百分比提升，各組的試片抗菌率基本上提升。並且，當含鋅牡蠣殼粉組別 (不論是添加硬脂酸鋅或碳酸鋅) 粉體重量百分比為2%時，可達到99.9%的抗菌率上限；當改質含鋅牡蠣殼粉組別於粉體的重量百分比為1%時，可達到99.9%的抗菌率上限。According to Table 2, it can be observed that among the test pieces of each group, as the weight percentage of the powder increases, the antibacterial rate of the test pieces of each group basically increases. And, when the zinc-containing oyster shell powder group (whether adding zinc stearate or zinc carbonate) powder weight percentage is 2%, the upper limit of 99.9% antibacterial rate can be reached; when the modified zinc-containing oyster shell powder group When the weight percentage of powder is 1%, the upper limit of antibacterial rate can reach 99.9%.
相對於無含鋅 (氧化鋅或還原態鋅) 的牡犡殼粉，本案的含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉 (脂肪酸改質) 組別，在添加相同重量百分比的粉體時，可以具有較高的抗菌率。此外，經脂肪酸改質的組別 (例如請參改質含鋅牡蠣殼粉 (2%硬脂酸改質，碳酸鋅重量份配比0.225) 以及改質含鋅牡蠣殼粉 (2%硬脂酸改質，碳酸鋅重量份配比0.333) )，相對於含鋅牡蠣殼粉，抗菌率進一步提升，主要原因在於，經硬脂酸改質處理，提升改質含鋅牡蠣殼粉於試片中的分散性，從而獲得較好的抗菌率。舉例而言，粉體重量百分比為1%時，牡犡殼粉的抗菌率為76.3%、含鋅牡蠣殼粉 (含鋅添加物為硬脂酸鋅) 的抗菌率為99.6%、含鋅牡蠣殼粉 (含鋅添加物為碳酸鋅) 的抗菌率為99.0%、改質含鋅牡蠣殼粉 (2%脂肪酸改質，碳酸鋅重量份配比0.225) 的抗菌率為99.8%。Compared with the oyster shell powder without zinc (zinc oxide or reduced zinc), the zinc-containing oyster shell powder and the modified zinc-containing oyster shell powder (fatty acid modified) group in this case were added with the same weight percentage of powder , can have a higher antibacterial rate. In addition, the group modified by fatty acid (for example, please refer to modified zinc-containing oyster shell powder (2% stearic acid modified, zinc carbonate weight ratio 0.225) and modified zinc-containing oyster shell powder (2% stearic acid Acid modification, zinc carbonate weight ratio 0.333) ), relative to the zinc-containing oyster shell powder, the antibacterial rate is further improved, the main reason is that, through the stearic acid modification treatment, the improved zinc-containing oyster shell powder is improved on the test piece Medium dispersion, so as to obtain a better antibacterial rate. For example, when the powder weight percentage is 1%, the antibacterial rate of oyster shell powder containing zinc is 76.3%, the antibacterial rate of oyster shell powder containing zinc (zinc stearate as the zinc additive) is 99.6%, and the antibacterial rate of oyster shell powder containing zinc The antibacterial rate of shell powder (zinc carbonate as zinc additive) was 99.0%, and the antibacterial rate of modified zinc-containing oyster shell powder (2% fatty acid modification, zinc carbonate weight ratio 0.225) was 99.8%.
2.2試片抗菌耐水性測試2.2 Antibacterial and water resistance test of test piece
2.2.1牡蠣殼粉、含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉的抗菌耐水性比較2.2.1 Comparison of antibacterial and water resistance of oyster shell powder, zinc-containing oyster shell powder and modified zinc-containing oyster shell powder
為測試各組抗菌耐水性 (在經水洗後，抗菌率是否改變)。將重量百分比為3%的測試粉體 (牡蠣殼粉、含鋅牡蠣殼粉或以2%硬脂酸改質的含鋅牡蠣殼粉)，以與2.1試片抗菌率測試相似的方式，製備出對應的試片，同樣以大腸桿菌為測試菌株，根據日本Boken的測試方法，執行抗菌耐水性測試 (包含耐水性1級測試以及耐水性2級測試)，結果請見表3。In order to test the antibacterial and water resistance of each group (after washing with water, whether the antibacterial rate changes). The test powder (oyster shell powder, zinc-containing oyster shell powder or zinc-containing oyster shell powder modified with 2% stearic acid) with a weight percentage of 3% was prepared in a manner similar to that of 2.1 test piece antibacterial rate test. The corresponding test piece was produced, and E. coli was also used as the test strain. According to the Japanese Boken test method, the antibacterial and water resistance test (including
註：Boken的測試方法的耐水1級測試，包含將5公分x5公分的試片靜置在50毫升的水中，溫度設定在25°C，18小時後取出試片，晾乾後根據前述2.1試片抗菌率測試的流程，執行抗菌率測試，檢驗水洗後試片的抗菌率。耐水2級測試的溫度則是將水的溫度提升至50°C。耐水1級與耐水2級結果代表試片的耐水範圍，其中耐水1級適用於很少接觸到水的情境 (會被濺到水)，耐水2級適用經常與水接觸的情境 (在水中放置或使用)。Note: The
表3、牡蠣殼粉、含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉的抗菌耐水性比較表
表3結果呈現，牡蠣殼粉經水洗後，抗菌率大幅下降，主要原因在於，習知牡蠣殼粉的氧化鈣可溶於水，因此牡蠣殼粉組別的試片接觸水，用於抗菌的氧化鈣流失，因此試片抗菌率遞減。相對而言，本案的含鋅牡蠣殼粉以及改質含鋅牡蠣殼粉 (脂肪酸改質) 的組別，抗菌耐水性較佳，並且改質含鋅牡蠣殼粉組別的抗菌耐水性微幅高於含鋅牡蠣殼粉組別。The results in Table 3 show that after the oyster shell powder is washed with water, the antibacterial rate drops significantly. Calcium oxide is lost, so the antibacterial rate of the test piece decreases. Relatively speaking, the group of zinc-containing oyster shell powder and modified zinc-containing oyster shell powder (fatty acid modification) in this case has better antibacterial and water resistance, and the antibacterial and water resistance of the modified zinc-containing oyster shell powder group is slightly Higher than zinc-containing oyster shell powder group.
2.2.2脂肪酸的添加量與改質含鋅牡蠣殼粉試片的抗菌耐水性的關係2.2.2 The relationship between the amount of fatty acid added and the antibacterial and water resistance of the modified zinc-containing oyster shell powder test piece
根據相似於2.2.1的耐水1級測試的流程，比較未添加粉體的試片、含鋅牡蠣殼粉以及經添加不同重量百分比硬脂酸改質的改質含鋅牡蠣殼粉(重量份配比0.333的碳酸鋅所製備而得，鋅含量152,454 ppm)所製備而得的試片，在水洗前後的抗菌率，結果請見表4。According to the flow process similar to the
表4、硬脂酸的添加量與改質含鋅牡蠣殼粉試片的抗菌耐水性比較表
表4結果呈現，在水洗處理後，相較於未添加硬脂酸改質的含鋅牡蠣殼粉，經硬脂酸改質的改質含鋅牡蠣殼粉組別，因分散性提升，故抗菌率提升，並且隨著硬脂酸的添加量提升，抗菌效果逐步提升。可以了解的是，由於2%的脂肪酸添加量，抗菌耐水性已可達99.99%，因此，若改質含鋅牡蠣殼粉以2%脂肪酸做為添加上限，可以在取得高抗菌耐水性的前提下，同時節省成本。The results in Table 4 show that after washing treatment, compared with the zinc-containing oyster shell powder without stearic acid modification, the modified zinc-containing oyster shell powder group modified with stearic acid has improved dispersibility, so The antibacterial rate increased, and with the addition of stearic acid, the antibacterial effect gradually increased. It can be understood that due to the addition of 2% fatty acid, the antibacterial and water resistance can reach 99.99%. Therefore, if the modified zinc-containing oyster shell powder is added with 2% fatty acid as the upper limit, it can achieve high antibacterial and water resistance. , while saving costs.
本揭示內容揭示含鋅牡蠣殼粉以及製備含鋅牡蠣殼粉的方法，經由煅燒含鋅添加物與牡蠣殼粉，成長含鋅奈米級粒子於牡蠣殼粉表面，相較於牡蠣殼粉，具有較好的抗菌效果以及抗菌耐水性。在一些實施方式中，經過乾式固態混合的步驟，相較於習知的濕式溶劑法，不僅避免廢液排放的環保問題，並且可省略因溶劑而衍申的後續處理步驟，簡化製備流程。This disclosure discloses zinc-containing oyster shell powder and a method for preparing zinc-containing oyster shell powder. By calcining zinc-containing additives and oyster shell powder, zinc-containing nano-sized particles are grown on the surface of oyster shell powder. Compared with oyster shell powder, It has good antibacterial effect and antibacterial water resistance. In some embodiments, the step of dry solid-state mixing, compared with the conventional wet solvent method, not only avoids the environmental protection problem of waste liquid discharge, but also omits the subsequent processing steps derived from the solvent, simplifying the preparation process.
另一方面，本揭示內容利用牡蠣殼粉做為含鋅添加物成長含鋅奈米級粒子的長晶載體，相較於直接經化學反應 (例如濕式溶劑法) 合成含鋅奈米級粒子，含鋅奈米級粒子分散性較佳。On the other hand, this disclosure uses oyster shell powder as a zinc-containing additive to grow zinc-containing nano-particles as a growth carrier, compared to directly synthesizing zinc-containing nano-particles through chemical reactions (such as wet solvent method) , better dispersion of zinc nanoparticles.
儘管本揭示內容已根據某些實施方式具體描述細節，其他實施方式也是可行的。因此，所附請求項的精神和範圍不應限於本文所記載的實施方式。While this disclosure has described details in terms of certain implementations, other implementations are possible. Therefore, the spirit and scope of the appended claims should not be limited to the implementations described herein.
100:方法 S110、S120、S130、S140:步驟 T1、T2、T3、T4:攪拌葉片 A1、A2、A3:箭頭 C0:含鈣核心 Z0:含鋅奈米級粒子 P:凹入點 100: method S110, S120, S130, S140: steps T1, T2, T3, T4: stirring blades A1, A2, A3: Arrows C0: calcium core Z0: Nanoparticles containing zinc P: concave point
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之詳細說明如下： 第1圖呈現本揭示內容的一些實施方式中製備含鋅牡蠣殼粉的方法； 第2A圖至第2B圖呈現本揭示內容的一些實施方式中製備含鋅牡蠣殼粉的攪拌葉片示例，其中第2A圖為攪拌葉片組裝示意圖，第2B圖為第2A圖中的個別攪拌葉片示意圖； 第3A圖至第3B圖呈現本揭示內容的一些實施方式中由不同攪拌條件所成長的含鋅奈米級粒子與牡蠣殼粉的電子顯微鏡影像，其中第3A圖的攪拌條件中葉片轉速採用600rpm、攪拌溫度採用90°C、攪拌時間採用60分鐘，第3B圖的攪拌條件大致上與第3A圖相近，與第3A圖的差異在於，攪拌溫度採用25°C； 第4圖呈現本揭示內容的一些實施方式中牡蠣殼粉的電子顯微鏡影像； 第5A圖至第5B圖呈現本揭示內容的一些實施方式中不同視角下的改質含鋅牡蠣殼粉的電子顯微鏡影像；以及 第6圖呈現本揭示內容的一些實施方式中改質含鋅牡蠣殼粉的X光繞射儀的分析結果。 In order to make the above and other objects, features, advantages and embodiments of the present invention more comprehensible, the detailed description of the accompanying drawings is as follows: Figure 1 presents a method of preparing zinc-containing oyster shell meal in accordance with some embodiments of the present disclosure; Figures 2A to 2B present examples of mixing blades for preparing zinc-containing oyster shell powder in accordance with some embodiments of the present disclosure, wherein Figure 2A is a schematic diagram of the assembly of the mixing blades, and Figure 2B is a schematic diagram of the individual mixing blades in Figure 2A ; Figures 3A to 3B present electron microscope images of zinc-containing nanoparticles and oyster shell powder grown under different agitation conditions in some embodiments of the present disclosure, wherein the agitation condition in Figure 3A is 600 rpm , Stirring temperature adopts 90 DEG C, stirring time adopts 60 minutes, the stirring condition of the 3B figure is roughly similar to the 3A figure, and the difference with the 3A figure is that the stirring temperature adopts 25 DEG C; Figure 4 presents an electron microscope image of oyster shell flour in accordance with some embodiments of the present disclosure; Figures 5A-5B present electron microscope images of modified zinc-containing oyster shell meal at different viewing angles in accordance with some embodiments of the present disclosure; and Figure 6 presents the results of an X-ray diffractometer analysis of modified zinc-containing oyster shell meal in accordance with some embodiments of the present disclosure.
100:方法 100: method
S110、S120、S130、S140:步驟 S110, S120, S130, S140: steps
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| TW111106745A TWI787091B (en) | 2022-02-24 | 2022-02-24 | Oyster shell powder and manufacture method thereof |
| CN202210270311.4A CN114568449B (en) | 2022-02-24 | 2022-03-18 | Oyster shell powder and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352676A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Preparation method of nano-zinc oxide with shell powder as carrier |
| TW201616970A (en) * | 2014-08-07 | 2016-05-16 | 歐米亞國際公司 | Antiseptic product, process for preparing same and its use |
| CN109966313A (en) * | 2019-04-19 | 2019-07-05 | 泉州师范学院 | A composite zinc oxide nanomaterial based on oyster shell or egg shell template, its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1125778C (en) * | 2000-08-25 | 2003-10-29 | 山东省海洋化工科学研究院 | Method for preparing metal oxide nano material |
| CN1239395C (en) * | 2002-01-22 | 2006-02-01 | 大连三科科技发展有限公司 | Process for preparing nano zinc oxide material |
| EP1621519A1 (en) * | 2004-07-28 | 2006-02-01 | SOLVAY (Société Anonyme) | Alkaline - earth metal carbonate core coated with at least one Group IV transition metal compound |
| CN106279762B (en) * | 2015-06-04 | 2018-06-15 | 陆昌化工股份有限公司 | Core-shell zinc oxide powder and ammonia type preparation method thereof |
| CN109938039A (en) * | 2019-04-19 | 2019-06-28 | 泉州师范学院 | A kind of preparation method and antibacterial application of CaO/ZnO composite nanomaterials |
| CN111265414B (en) * | 2019-11-06 | 2022-08-05 | 成都理工大学 | Kaolinite loaded nano ZnO composite anti-ultraviolet agent and preparation method thereof |
| CN111467251B (en) * | 2019-11-06 | 2022-08-05 | 成都理工大学 | Calcined kaolin loaded nano ZnO composite anti-ultraviolet agent and preparation method thereof |
| CN113881249B (en) * | 2021-11-24 | 2023-02-03 | 吴振清 | Oyster shell powder composite filler with superhydrophobicity and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352676A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Preparation method of nano-zinc oxide with shell powder as carrier |
| TW201616970A (en) * | 2014-08-07 | 2016-05-16 | 歐米亞國際公司 | Antiseptic product, process for preparing same and its use |
| CN109966313A (en) * | 2019-04-19 | 2019-07-05 | 泉州师范学院 | A composite zinc oxide nanomaterial based on oyster shell or egg shell template, its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 期刊 , X LIU, et al., "Preparation of integrated CuO/ZnO/OS nanocatalysts by using acid-etched oyster shells as a support for CO2 hydrogenation", ACS Sustainable Chem. Eng., 8, ACS Publications, 2020: 7162~7173. * |
Also Published As
| Publication number | Publication date |
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| TW202333574A (en) | 2023-09-01 |
| CN114568449A (en) | 2022-06-03 |
| CN114568449B (en) | 2024-02-23 |
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