WO2017050264A1 - 一种新型可控型的层状结构的纳米钻石烯 - Google Patents

一种新型可控型的层状结构的纳米钻石烯 Download PDF

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WO2017050264A1
WO2017050264A1 PCT/CN2016/099791 CN2016099791W WO2017050264A1 WO 2017050264 A1 WO2017050264 A1 WO 2017050264A1 CN 2016099791 W CN2016099791 W CN 2016099791W WO 2017050264 A1 WO2017050264 A1 WO 2017050264A1
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nanodiamondene
ene
nano diamond
carbon atoms
diamond
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PCT/CN2016/099791
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English (en)
French (fr)
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郭留希
赵清国
张洪涛
杨晋中
刘永奇
武艳强
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郑州华晶金刚石股份有限公司
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Publication of WO2017050264A1 publication Critical patent/WO2017050264A1/zh

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  • the present invention belongs to the field of nano carbon materials, and particularly relates to a novel controllable layered structure of nanodiamondene.
  • Carbon nanomaterials refer to carbon materials whose particle size is in the nanometer scale range. It has the special properties of nanomaterials, which makes it have the potential for special performance applications. Nanodiamonds not only have the inherent properties of diamond, but also have the specific properties of nanomaterials, such as large specific surface area and small size effects. At present, the synthesis of nanodiamonds visible on the market is synthesized by the explosion method. This synthesis technology mainly uses the negative oxygen balance explosives, and under the action of the protective medium, the high temperature and high pressure generated by the explosion moment (2000K-3000K, 20GPa) -30 GPa) converts free carbon into diamond. The characteristics of nano-diamond synthesized by this method are: 1.
  • the particles are in a hard agglomerated state and cannot be dispersed. 3.
  • Synthesis The process is complicated and the subsequent processing is cumbersome. So far, there is no way to solve the problem of the dispersion of the nano-diamond in the explosion method, thus limiting the further application of the nano-diamond.
  • the morphology of artificial graphite and graphene is a product of a sheet structure, and the preparation methods of the two C materials are complicated.
  • the preparation process of artificial graphite is complicated, using petroleum coke, asphalt coke and other materials, as well as asphalt binder, calcined, compounded, kneaded, pressed, calcined, impregnated, graphitized, machined, calcined
  • the temperature is very high, and high temperature treatment is required in a non-oxidizing environment. It takes about 3000 ⁇ 3300 °C to recrystallize the amorphous C atoms into graphite crystals.
  • the industrial preparation method of graphene is mainly a redox method, which oxidizes graphite by an oxidant, increases the interlayer spacing of graphite, separates it by physical methods, and finally obtains graphene by chemical method, thereby obtaining the graphene.
  • Graphene production is high, but product quality is low.
  • a novel controllable layered structure of nanodiamondene is a lamellar single crystal structure, and sp 3 orbital impurities are present between carbon atoms of the same layer.
  • the carbon bond is connected, and the carbon atoms between the layers are sp 2 orbital hybrid carbon bonds.
  • the nanodiamondene has a lattice spacing of 0.21 nm.
  • the average particle diameter is R, 20 ⁇ R ⁇ 500 nm.
  • the nanodiamondene has a C content of 99 to 100%.
  • Preliminary crushing The diamond raw material is sent into a ball-shaping plastic barrel to crush and sift out particles of 70 mesh or more, and the crushed concrete is l-5h, and the coarse material below 70 mesh is returned to the ball-shaping plastic barrel for re-crushing;
  • the fine material of 800 mesh or more is sieved by a multi-stage vibrating sieve machine, and the vibrating screen is 30 min-2 h, and the fine material is repeatedly sieved more than once.
  • the nanodiamondene provided by the present invention has the following advantages:
  • the nanodiamondene of the present invention has a high particle concentration degree, a narrow particle size range distribution, and a controllable particle size, and a nanodiamondene having a particle diameter in the range of 20 to 500 nm can be prepared as needed.
  • the shape of the nano-diamondene is a multi-layered sheet structure, the morphology is controllable, the dispersibility is good, no agglomeration occurs, and the particle size is proportional to the thickness of the sheet, and the same layer is
  • the carbon atoms are connected by sp 3 orbital hybrid carbon bonds, the carbon atoms between the layers are sp 2 hybrid carbon bonds, and the sp 2 hybrid orbital carbon bonds
  • the nano-diamondene provided by the invention is a good storage material and can be used as a super storage battery.
  • the single-layer flake-shaped diamond olefin has high hardness and wear resistance, but the layer is easy to slide and cleave between the layers, and has high self-lubricity, and the same as the lubricant is also cleaned and further Polishing and other effects.
  • the C content is 99 to 100%, the crystallinity is very strong, and has no toxic and side effects to the human body. It can be used for the preparation of bionic materials such as human teeth, bones, joints, and surface treatment thereof, and can be used for preparing artificial teeth and artificial Bones, prostheses, etc.
  • an outer space optical device can be prepared, or it can be coated as a coating material on the surface of other objects, and can also function as a heat insulator while absorbing a good visible light.
  • a novel controllable layered structure of nanodiamondene is a lamellar single crystal structure, wherein the carbon atoms of the same layer are sp 3 orbital hybrid carbon bonds, between layers The carbon atoms are sp 2 hybridized with carbon bonds; the particle size is R, 20 ⁇ R ⁇ 500 nm, the C content is 99 to 100 ⁇ 3 ⁇ 4, and the lattice spacing is 0.21 nm.
  • Preliminary crushing The diamond raw material is sent into the ball-shaping plastic bucket, and the steel balls of different particle sizes are passed. After the ball milling and crushing process under high-speed rotation, the ball mill receiving port is collected through a screen of a certain mesh size, the mesh number of the mesh is not less than 70 mesh, and the ball milling and shaping is generally controlled at l-5h. 70 mesh coarse material is automatically returned to the ball mill for re-ball milling; the collected particles above 70 mesh are subjected to multi-layer vibrating sieve for initial particle size distribution, and the mesh mesh number is from 100 mesh to 800 mesh in order from high to low. The vibrating screen is usually between 30min and 2h. Finally, the 800-mesh screen is used to filter the fine material. The rest of the particle size is used for other purposes. In order to ensure the accuracy of the particle size, the vibrating material should be re-grown. Perform vibration screening.
  • (3) pickling firstly, the fine powder is pickled in a mixture of concentrated sulfuric acid and concentrated nitric acid for 2-7 hours, filtered and washed, and the mixed solution of concentrated sulfuric acid and concentrated nitric acid has a mass fraction of 98% concentrated sulfuric acid.
  • the mass fraction of 10% concentrated nitric acid is mixed according to the mass ratio of 5:1; then the fine powder is placed in the dilute hydrochloric acid of 140 ° C ⁇ 160 ° C with a mass fraction of 5% ⁇ 8 ⁇ 3 ⁇ 4 for 4-9 h, filtered Then put the fine powder in hydrofluoric acid for 10 ⁇ 20 h, remove the metal impurities in the material and the impurities attached to the material during the ball milling and air flow breaking process, and then wash it with deionized water until the pH of the cleaning solution is close.
  • hydrofluoric acid for 10 ⁇ 20 h
  • the washed material is subjected to centrifugal sorting.
  • the centrifugal sorting is to control the particle size by using the rotating speed and the centrifugal chamber. The higher the rotating speed, the longer the material obtained by the centrifugal chamber is. The finer the particle size is, the centrifugation time is 30 ⁇ 50min, and the rotation speed is 8000rpm.
  • the upper part of the centrifuge tube is sedimented and sorted for 5 days.
  • the sediment at the bottom of the centrifuge tube can be recycled as coarser material. For sale, it can be re-refined into nano-diamondene.
  • the precipitation separation can control the particle size by controlling the length of the precipitate. The larger the particle size, the shorter the sedimentation time. After the sedimentation, the supernatant is removed, and the lower layer is precipitated.
  • the finished product is obtained after the particle size is tested and dried to obtain the finished nano-diamondene.
  • the novel controllable layered structure of nanodiamondene prepared by the above method is a lamellar single crystal structure, and the carbon atoms of the same layer are sp 3 orbital hybrid carbon bonds, and the layer Between the carbon atoms between the layers is a sp 2 hybrid carbon bond;
  • C content is 99 ⁇ 100 ⁇ 3 ⁇ 4, lattice spacing is 0.21nm, particle size is 200 ⁇ 500nm, each of which is described here.
  • the particle size value is a particle diameter peak in a small range, and the particle diameter of the peak is at least 98% or more in the particle size sorted between the corresponding sorting cells.
  • Example 3 The preparation process of Example 3 is different from that of Example 2 in that: the centrifugal day is 2 h, the rotation speed is 8000 rp m, and the sedimentation time is 1 day.
  • the prepared nanodiamondene has a particle diameter of 100 to 200 nm.
  • Example 4 The preparation process of Example 4 is different from that of Example 2 in that: the centrifugation time is lh, the rotation speed is lOOOOr pm, and the precipitation separation time is 4 days.
  • the prepared nanodiamondene has a particle diameter of 50 to 100 nm.
  • Example 5 The preparation process of Example 5 is different from that of Example 2 in that: the centrifugal chamber is 2 h, the rotation speed is 20000 rpm, and the precipitation separation time is 7 days.
  • the prepared nanodiamondene has a particle diameter of 20 to 50 nm.
  • Example 1 is a: explosive nanodiamond; b: novel nanodiamondene prepared in Example 2; c: graphite; d: XRD spectrum of graphene.
  • the novel nanodiamondene prepared by the present invention is a carbon nanosheet having a diamond phase structure, and the diffraction main peak of the novel nanodiamondene prepared by the present invention can be seen from the XRD spectrum.
  • the diffraction intensity of 111) is much larger than that of the nano-diamond synthesized by the explosion method, indicating that the crystallites prepared by the present invention are far more crystalline than the nano-diamonds synthesized by the explosion method.
  • ⁇ is a constant
  • ⁇ is a full width at half maximum
  • the diamond olefin grain size prepared by the invention is about 5 times that of the nano-diamond synthesized by the explosion method, which means that the diamond olefin prepared by the invention is distorted in the carbon atom structure.
  • Small, good crystallinity because the smaller the crystallite, the more likely it is to cause lattice distortion, which is more advantageous for expanding the application range of nanodiamond.
  • 2 is a: explosive nanodiamond; b: novel nanodiamondene prepared in Example 2; c: graphite; d: TEM analysis of graphene.
  • the corresponding 1 is a partial enlarged view, 2 is the corresponding HRTEM image, and the upper left corner of the 1 figure is the corresponding SAED image.
  • the morphology of the novel nano-diamondene prepared by the present invention is different from other carbon materials, and is a multi-layered sheet structure, which can be seen from the SAED diagram in the upper left corner of FIG.
  • the diamond olefin prepared by the invention is a single crystal structure, and the nano diamond prepared by the explosion method is composed of agglomerated particles and has a polycrystalline structure, and both graphite and graphene have a sheet-like structure.
  • the structure is different from the diamond arene prepared by the present invention.
  • the diamond arene prepared by the present invention has a sheet length of 200-500 nm, and the graphite and graphene sheets have a length longer than ⁇ , and the thickness is also thicker than graphite or graphene. It can also be seen from the SAED diagram that although single crystal electron diffraction is exhibited, the SAED pattern of graphite and graphene is a typical hexagonal SAED pattern, which is different from the diamondene prepared by the present invention, which indicates the preparation of the present invention. Diamond olefins have different crystal structures from graphite and graphene.
  • the lattice spacing is 0.21 nm, which is close to the diamond phase (111) plane lattice spacing of 0.206 nm, which indicates that the products of the sheet structure are all along the (111) plane. From the figure, we can also see that the new nano-diamondene dispersibility is much better than that of the nano-diamond prepared by the explosion method, and the specific surface area is large, and it is easier to adsorb other functional groups on the surface, thereby realizing the functional treatment of the diamond surface and expanding its Application range.
  • Example 3 is a: MAS-NMR of the novel nanodiamondene prepared in Example 2, b: explosive nanodiamond analysis.
  • the novel nano-diamondene prepared by the invention has a layered structure, and the nano-diamond synthesized by the explosion method is composed of two different carbon CC 2s , wherein C and carbon have peak positions and The diamond olefins produced by the invention are different, which indicates that there are some differences in the arrangement of carbon atoms in the two kinds of nanodiamonds.
  • the novel nanodiamondene prepared by the invention has two different carbon structures, sp 3 orbital hybrid carbon and sp 2 orbital hybrid carbon, and the sp 3 orbital hybrid carbon bond between the carbon atoms of the same layer, the layer and The carbon atoms between the layers are sp 2 hybridized carbon bonds, so that there are many electron vacancies between the layers, and the electron vacancies facilitate electrons to enter and exit.
  • the sp 3 orbital hybrid carbon is The three-dimensional structure of hybrid carbon, sp 2 orbital hybrid carbon is a planar structure of hybrid carbon which is different from the carbon structure of the nano-diamond synthesized by the explosion method.
  • Graphene has a two-dimensional crystal structure, its crystal lattice is a hexagon composed of six carbon atoms, the bonding mode between carbon atoms is sp 2 orbital hybridization, and graphite is six carbon atoms in the same layer.
  • the hexagonal shape of the composition, the bonding mode between the carbon atoms of the same layer is that the sp 2 orbital hybridization forms a chemical bond, and the layer is connected by van der Waals force, and the carbon atoms in the nanotube are hybridized by sp 2 orbital.
  • the same enthalpy also has a certain curvature, which can form a certain sp 3 hybrid bond, that is, the chemical bond formed in the same curved surface has the mixed state of sp 2 and sp 3 , and the carbon atom of these carbon materials
  • the arrangement is different from the novel nanodiamondene prepared by the present invention.
  • 5 is a Raman spectrum of nanodiamondene, (a) particle diameter 250 nm; (b) particle diameter 200 nm; (c) particle diameter 100 nm; (d) particle diameter 50 nm.
  • the synthesized layered diamondene of different particle diameters has a similar Raman spectrum of the nanodiamond synthesized by the explosion method, but differently, as the particle size of the sample changes, Raman Spectrograms also change regularly, and the intensity of the D peaks and G peaks of the two main peaks is gradually weakening. This is mainly due to the change of the structure of the sample itself.
  • the sp 2 carbon and sp 3 carbon carbon atoms constitute A special dimer structure. As the particle size of the sample changes, the content of this particular dimer structure gradually increases, resulting in the gradual weakening of the intensity of the two main diffraction peaks. This special property may give nanodiamonds. Apply a broader application.
  • the novel multilayer structure diamond olefin of the present invention can be widely used in coating agents after surface functionalization (wear-resistant coating, heat-resistant anti-oxidation coating, corrosion-resistant coating, functional coating, etc.) ), self-cleaning agent, polymer , plastic, rubber, leather, leather sole treatment, fiber, glass (car windshield, mobile phone screen, etc.), mobile phone screen protector, mobile phone case, mobile phone back cover, ceramic, kitchen countertop, steel surface treatment agent, Stainless steel surface treatment, non-stick pan, conductive contacts, automotive heat sink, automotive brake pads, bearings, bearing surface treatment agents, automotive lubricants, automotive antifreeze, automotive plastics, spectacle frame finishers, lens cleaners, abrasive pastes , grinding fluids, daily necessities (such as toothpaste, soap, soap, shower gel, detergent, toilet net, etc.), cosmetics (cleanser, shampoo, etc.), drug targeting agents, optoelectronic devices, biosensor probes, sensors, Lithium-ion batteries, supercapacitors, computer CPUs, displays

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Abstract

提供一种可控型的层状结构的纳米钻石烯，为层片状单晶结构，同一片层的碳原子之间为sp3轨道杂化碳键连接，层与层之间的碳原子之间为sp2杂化碳键连接；粒径为20-500nm，C含量为99～100％。该纳米钻石烯形貌为多层片状结构，形貌可控，分散性好，无抱团团聚现象发生，且粒径与片厚存在比例关系，层与层之间有许多电子空位，电子空位方便电子自由出入。

Description

一种新型可控型的层状结构的纳米钻石烯 技术领域
[0001] 本发明属于纳米碳材料领域， 具体涉及一种新型可控型的层状结构的纳米钻石 烯。
背景技术
[0002] 碳纳米材料是指样品粒径在纳米尺度范围内的碳材料， 它具有纳米材料的特殊 性质， 使其具有特殊性能应用的幵发潜力。 纳米金刚石不仅具备金刚石所具有 的固有性能， 同吋还具有纳米材料的特异性能， 例如比表面积大、 小尺寸效应 等。 目前市场上可见的纳米金刚石的合成都是采用爆炸法合成制备的， 这种合 成技术主要是利用负氧平衡炸药， 在保护介质的作用下， 通过爆炸瞬间产生的 高温高压 (2000K-3000K, 20GPa-30 GPa)将游离碳转化成金刚石， 这种方法合成 的纳米金刚石的特点是： 1、 形貌单一不规则且为团聚的颗粒； 2、 颗粒呈硬团 聚状态， 无法进行分散， 3、 合成过程比较复杂， 后续处理过程也比较繁琐， 到 目前为止并没有一种方法能够解决爆炸法纳米金刚石的分散问题， 从而限制了 纳米金刚石的进一步的扩展应用。
[0003] 目前在 C材料中， 人造石墨及石墨烯的形貌是一种片状结构的产物， 这两种 C 材料制备工艺方法较为复杂。 人造石墨的制备工艺较为复杂， 采用石油焦碳、 沥青焦碳等 c素材料， 以及沥青粘结剂， 经煅烧、 配料、 混捏、 压型、 焙烧、 浸 渍、 石墨化、 机加工而成， 煅烧温度很高， 而且需在非氧化环境中进行高温处 理， 约需 3000〜3300°C才能将无定型的 C原子经过重新排布晶化成石墨晶体。 而 石墨烯的工业制备工艺方法主要是氧化还原法， 通过氧化剂将石墨氧化， 增大 石墨的层间距， 再通过物理方法将其分离， 最后通过化学法进行还原得到石墨 烯， 这种方法得到的石墨烯产量高， 但是产品质量低。
技术问题
[0004] 本发明的目的在于提供一种新型可控型的层状结构的纳米钻石烯。
问题的解决方案 技术解决方案
[0005] 基于上述目的， 本发明采用以下技术方案： 一种新型可控型的层状结构的纳米 钻石烯， 为层片状单晶结构， 同一片层的碳原子之间为 sp 3轨道杂化碳键连接， 层与层之间的碳原子之间为 sp 2轨道杂化碳键连接。
[0006] 优选地， 该纳米钻石烯的晶格间距为 0.21nm。
[0007] 优选地， 平均粒径为 R， 20≤R≤500nm。
[0008] 优选地， 该纳米钻石烯的 C含量为 99〜100%。
[0009] 上述纳米钻石烯采用以下制备工艺， 步骤为：
[0010] ( 1) 初步破碎： 将金刚石原料送入球磨整形桶内破碎筛出 70目以上的颗粒， 破碎吋间为 l-5h， 70目以下的粗料返回球磨整形桶进行重新破碎； 颗粒经多级振 筛机筛分出 800目以上的细料， 振筛吋间为 30min-2h， 该细料重复过筛一次以上
[0011] (2) 再次破碎： 将筛分出 800目以上细料输送至气流破碎机内， 利用高压气流 对细料粉碎后筛分出 8000目以上的细粉， 筛余物返回气流破碎机进行重新破碎
[0012] (3) 酸洗： 将 8000目以上的细粉经过酸洗提纯后， 使用去离子水清洗至清洗 液 pH接近于 7 ;
[0013] (4) 分选： 将清洗后的物料进行离心分离， 取上层液体进行 1-5天沉淀分选， 去除上层清液， 将下层沉淀物干燥后即得成品纳米钻石烯； 离心分离步骤中， 离心吋间为 30min-2h， 转速为 8000rpm- 15000rpm。
发明的有益效果
有益效果
[0014] 与现有技术相比， 本发明提供的纳米钻石烯具有以下优点：
[0015] ( 1) 本发明的纳米钻石烯粒径集中度高， 粒径范围分布窄， 粒径大小可控， 可根据需要制备粒径在 20-500nm范围内的纳米钻石烯。
[0016] (2) 该纳米钻石烯形貌为多层片状结构， 形貌可控， 分散性好， 无抱团团聚 现象发生， 且粒径与片厚存在比例关系， 同吋同一片层的碳原子之间为 sp 3轨道 杂化碳键连接， 层与层之间的碳原子之间为 sp 2杂化碳键连接， sp 2杂化轨道碳键 为不饱和建， 使层与层之间有许多电子空位， 电子空位方便电子自由出入， 因 此采用本发明提供的纳米钻石烯是良好的储电材料， 可作为超级存储电池。
[0017] (3) 单层片状钻石烯硬度高且耐磨， 但是层与层之间容易滑动解理， 具有很 高的自润滑性， 在做润滑剂的同吋还起到了清理和进一步抛光等作用。
[0018] (4) C含量为 99〜100%， 结晶性非常强， 对人体无毒副作用， 可用于人体牙 齿、 骨头、 关节等仿生材质的制备以及其表面处理， 可用于制备人造牙齿、 人 造骨头、 假肢等方面。
[0019] (5) Raman测试结果表明， 随着钻石烯粒径的减小， 钻石烯的特征峰的峰强 也逐渐减弱， 这种与粒径匹配光致发光效应使得其在一些特殊光学领域有广泛 的应用。 例如可以制备外太空光学器件， 也可以将其作为涂层材料覆盖在其他 物体表面， 在很好的吸收了可见光的同吋还能起到隔热的作用等。
对附图的简要说明
附图说明
[0020] 图 1是纳米钻石烯的 XRD谱图；
[0021] 图 2是纳米钻石烯的 TEM分析图；
[0022] 图 3是纳米钻石烯的 MAS-NMR谱图；
[0023] 图 4是纳米钻石烯的原子轨道示意图；
[0024] 图 5是纳米钻石烯的 Raman光谱。
本发明的实施方式
[0025] 下面结合实施例对本发明进行详细说明。
[0026] 实施例 1
[0027] 一种新型可控型的层状结构的纳米钻石烯， 为层片状单晶结构， 同一片层的碳 原子之间为 sp 3轨道杂化碳键连接， 层与层之间的碳原子之间为 sp 2杂化碳键连接 ； 粒径为 R， 20<R≤500nm, C含量为 99〜100<¾， 晶格间距为 0.21nm。
[0028] 实施例 2
[0029] 上述纳米钻石烯采用以下工艺制备， 其步骤为：
[0030] (1) 初步破碎： 将金刚石原料送入球磨整形桶中， 经过不同粒径大小的钢球 在高速转动下的来回球磨破碎整形过程后， 在球磨机收料口通过一定筛网目数 的筛网进行收集， 筛网的目数不低于 70目， 球磨整形吋间一般控制在 l-5h， 70目 粗料自动返回球磨机重新进行球磨整形； 将收集的 70目以上的颗粒经过多层振 筛机进行粒径初分， 筛网目数从 100目到 800目依次由高到低排布， 振筛吋间一 般在 30min-2h， 最后收集 800目筛网过滤后的细料， 其余粒径的料另作它用， 同 吋为保证粒径的准确性需将振筛好的料重新进行振动筛分。
[0031] (2) 再次破碎： 将步骤 （1) 收集的 800目以上细料放入气流破碎机进料口后 进入气流破碎腔内， 利用高压气流对料进行破碎， 在气流破碎机收料口收集经 过筛网后的料， 筛网的目数从 1000目到 8000目从高到低依次排布， 收集 8000目 筛网过滤的细料， 1000目筛网收集的料自动返回气流破碎机破碎， 而其它目数 筛网收集的料可作为粗粒径的料出售或再次返回气流破碎机内重新破碎。
[0032] (3) 酸洗： 首先将细粉置于浓硫酸与浓硝酸混合液中酸洗 2~7h、 过滤、 清洗 ， 所述浓硫酸与浓硝酸混合液由质量分数为 98%浓硫酸和质量分数为 10%浓硝酸 按照质量比为 5: 1混合而成； 然后将细粉置于 140°C~160°C质量分数为 5%~8<¾的稀 盐酸中 4~9h、 过滤； 再将该细粉置于氢氟酸中 10~20 h， 去除料中的金属杂质以 及在球磨整形、 气流破碎过程中附着在料上的杂质， 然后使用去离子水清洗至 清洗液 pH接近于 7。
[0033] (4) 分选： 将清洗后的物料进行离心分选， 离心分选是利用转速和离心吋间 来达到对粒径的控制， 转速越高， 离心吋间越长得到的料的粒径就越细， 离心 吋间为 30~50min， 转速为 8000rpm; 离心分选后对离心管上部混合液进行沉淀分 选 5天， 离心管底部的沉积料可作为较粗粒径的料回收出售， 也可重新细化成纳 米钻石烯， 沉淀分选通过控制沉淀吋间的长短来达到控制粒径的目的， 粒径越 大沉淀吋间越短， 沉淀分选后去除上层清液， 下层沉淀物经粒径检测合格后烘 干后即可得到成品纳米钻石烯。
[0034] 利用上述方法制备出的新型可控型的层状结构的纳米钻石烯， 为层片状单晶结 构， 同一片层的碳原子之间为 sp 3轨道杂化碳键连接， 层与层之间的碳原子之间 为 sp 2杂化碳键连接；
C含量为 99〜100<¾， 晶格间距为 0.21nm， 粒径为 200~500nm， 该处所述的每一个 粒径值为一个很小的范围内的粒径峰值， 该峰值的粒径在对应的分选吋间分选 出的粒径中所占的比例至少在 98%以上。
[0035] 实施例 3
[0036] 实施例 3的制备工艺与实施例 2的不同之处在于： 离心吋间为 2h， 转速为 8000rp m， 沉淀分选吋间为 1天。 制备出的纳米钻石烯的粒径为 100~200nm。
[0037] 实施例 4
[0038] 实施例 4的制备工艺与实施例 2的不同之处在于： 离心吋间为 lh， 转速为 lOOOOr pm， 沉淀分选吋间为 4天。 制备出的纳米钻石烯的粒径为 50~100nm。
[0039] 实施例 5
[0040] 实施例 5的制备工艺与实施例 2的不同之处在于： 离心吋间为 2h， 转速为 20000r pm， 沉淀分选吋间为 7天。 制备出的纳米钻石烯的粒径为 20~50nm。
[0041] 性能测试
[0042] (1) XRD分析
[0043] 图 1是 a:爆炸法纳米金刚石； b: 实施例 2制备的新型纳米钻石烯； c: 石墨； d: 石墨烯的 XRD谱图。
[0044] 由图 1的 XRD谱图可知， 通过 X射线粉末衍射仪 (Cu Kot射线， 管电压 40Kv， 管 电流 40mA， λ=1.54056人)测试表明， 本发明制备的的新型纳米钻石烯在衍射角 2Θ =43.93°和 75.3°可以看到非常明显地衍射峰， 与典型的金刚石相衍射峰 (111)、 (22
0)相对应， 可以证明本发明制备的的新型纳米钻石烯是具有金刚石物相结构的碳 纳米片， 同吋从 XRD谱图上可以看出本发明制备的的新型纳米钻石烯的衍射主 峰 (111)的衍射强度远大于爆炸法合成的纳米金刚石， 说明本发明制备的的钻石 烯结晶性远比爆炸法合成的纳米金刚石强。 同吋可以看出石墨烯和石墨在衍射 角 2Θ=26.3°可以看见明显地衍射峰， 与典型的石墨烯和石墨衍射峰 (002)对应， 与 本发明制备的的新型纳米钻石烯出峰位置不同， 这说明本发明制备的的新型纳 米钻石烯与石墨、 石墨烯的物相构成是不同的， 碳纳米管的主衍射峰的出峰位 置为 26.4°， 对应的晶面为 (002)， 这与本发明制备的的钻石烯也是不同的。 根据 谢乐公式 [数] 灣
， κ为常数， β为半高宽， 本发明制备的的钻石烯晶粒大小是爆炸法合成的纳米 金刚石的 5倍左右， 这意味着本发明制备的的钻石烯在碳原子结构上畸变很小， 结晶性良好， 因为晶粒越小越容易产生晶格畸变， 这对于扩大纳米金刚石的应 用范围更为有利。
[0045] (2) ΤΕΜ分析
[0046] 图 2是 a: 爆炸法纳米金刚石； b: 实施例 2制备的新型纳米钻石烯； c: 石墨； d ： 石墨烯的 TEM分析图。 对应的 1为局部放大图， 2为对应的 HRTEM图， 1图左 上角插图为对应的 SAED图。
[0047] 由图 2可以明显地看出本发明制备的的新型纳米钻石烯的形貌区别于其它碳材 料， 而且是一种多层片状结构， 从 1图左上角的 SAED图我们可以看出， 本发明 制备的的钻石烯是一种单晶结构， 而爆炸法制备的纳米金刚石是团聚的颗粒组 成的， 且为多晶结构， 石墨和石墨烯均为片状结构， 这种片状结构与本发明制 备的的钻石烯不同， 本发明制备的的钻石烯的片长在 200-500nm之间， 石墨和石 墨烯的片长在 ΙΟμηι以上， 而且厚度也比石墨、 石墨烯要厚。 从 SAED图我们也可 以看出， 虽然都呈现单晶电子衍射， 但石墨和石墨烯的 SAED图是典型的六角晶 系的 SAED图， 不同于本发明制备的钻石烯， 这说明本发明制备的钻石烯与石墨 、 石墨烯具有不同的晶体结构。
[0048] 从 HRTEM图可以看出晶格间距均为 0.21nm， 与金刚石相 (111)面晶格间距 0.206 nm接近， 这说明这种片状结构的产物都是沿着 (111)面的， 从图中我们还可以看 出新型纳米钻石烯分散性远比爆炸法制备的纳米金刚石要好， 且比表面积大， 更加容易在表面上吸附其它官能团， 从而实现对金刚石表面的功能化处理， 扩 大其应用范围。
[0049] (3) MAS-NMR分析
[0050] 图 3是 a: 实施例 2制备的新型纳米钻石烯、 b: 爆炸法纳米金刚石的 MAS-NMR 分析。
[0051] 由图 3可以看出本发明制备的新型纳米钻石烯为层状结构， 爆炸法合成的纳米 金刚石是由两种不同的碳 C C 2构成的， 其中 C ,碳的出峰位置与本发明制备的 的钻石烯不同， 这说明这两种纳米金刚石里面的碳原子排布存在着一定的差别
。 本发明制备的新型纳米钻石烯是具有 sp 3轨道杂化碳和 sp 2轨道杂化碳两种不同 的碳结构， 同一片层的碳原子之间为 sp 3轨道杂化碳键连接， 层与层之间的碳原 子之间为 sp 2杂化碳键连接， 使层与层之间有许多电子空位， 电子空位方便电子 自由出入， 其中， 如图 4所示， sp 3轨道杂化碳是立体结构的杂化碳， sp 2轨道杂 化碳是平面结构的杂化碳这与爆炸法合成的纳米金刚石的碳结构是不同的。 而 石墨烯具有一种二维晶体结构， 它的晶格是由六个碳原子组成的六边形， 碳原 子之间的结合方式是 sp 2轨道杂化， 石墨是同层的六个碳原子组成的六边形， 同 层的碳原子之间的结合方式是 sp 2轨道杂化形成化学键， 而层与层之间是靠范德 华力连接的， 纳米管中的碳原子以 sp 2轨道杂化为主， 同吋还存在着一定的弯曲 ， 可形成一定的 sp 3杂化键， 即在同一弯曲面内形成的化学键同吋具有 sp 2和 sp 3 混合杂化状态， 这些碳材料的碳原子排布均不同于本发明制备的的新型纳米钻 石烯。
[0052] (4) Raman光谱分析
[0053] 图 5是纳米钻石烯的 Raman光谱图， （a) 粒径 250nm; (b) 粒径 200nm; (c ) 粒径 lOOnm; (d) 粒径 50nm。
[0054] 从图 5可以看出， 合成的不同粒径的层状结构的钻石烯具有爆炸法合成的纳米 金刚石类似的 Raman光谱图， 但是与其不同的是， 随着样品粒径的变化， Raman 光谱图也发生着规律性的变化， 其两个主峰 D峰和 G峰的强度逐渐在减弱， 这主 要是由于样品本身的结构发生了改变， sp 2碳和 sp 3碳两种碳原子构成了一种特殊 的二聚体结构， 随着样品粒径的变化， 这种特殊的二聚体结构含量逐渐增大导 致两个主衍射峰强度逐渐减弱， 这种特殊的性能可能会给纳米金刚石的应用打 幵更为广阔的应用。
[0055] 本发明的新型多层结构钻石烯经过表面功能化处理后， 可广泛使用于涂层剂（ 耐磨损涂层、 耐热抗氧化涂层、 耐腐蚀涂层、 功能性涂层等)、 自净剂、 聚合物 、 塑料、 橡胶、 皮革、 皮鞋鞋底表面处理剂、 纤维、 玻璃 (汽车挡风玻璃、 手机 屏等)、 手机屏保护剂、 手机保护壳、 手机后盖、 陶瓷、 厨房台面、 钢铁表面处 理剂、 不锈钢表面处理、 不粘锅、 导电触头、 汽车散热片、 汽车刹车片、 轴承 、 轴承表面处理剂、 汽车润滑油、 汽车防冻液、 汽车塑料、 眼镜架表面处理剂 、 镜片清洗剂、 研磨膏、 研磨液、 日用品 (如牙膏、 肥皂、 香皂、 沐浴露、 洗洁 精、 厕净等)、 化妆品 (洗面奶、 洗发剂等)、 药物靶向剂、 光电器件、 生物感应 探头、 传感器、 锂离子电池、 超级电容器、 电脑 CPU、 显示器、 超导材料、 导线 表面处理剂、 LED衬底、 电镀刷镀剂、 人体仿生材料、 人类牙齿修复及表面处理 、 牙齿打磨剂、 漱口剂、 洗手液、 人体关节修复及处理、 人体骨头修复及处理 、 人体血液清除剂、 人体肠道清除剂、 人体死皮去除剂、 人体毛孔修复剂、 心 血管支架等方面。

Claims

权利要求书
[权利要求 1] 一种新型可控型的层状结构的纳米钻石烯， 其特征在于， 为层片状单 晶结构， 同一片层的碳原子之间为 sp 3轨道杂化碳键连接， 层与层之 间的碳原子之间为 sp 2轨道杂化碳键连接。
[权利要求 2] 根据权利要求 1所述的新型可控型的层状结构的纳米钻石烯， 其特征 在于， 该纳米钻石烯的晶格间距为 0.21nm。
[权利要求 3] 根据权利要求 1或 2所述的新型可控型的层状结构的纳米钻石烯， 其特 征在于， 平均粒径为 R， 20≤R≤500nm。
[权利要求 4] 根据权利要求 3所述的新型可控型的层状结构的纳米钻石烯， 其特征 在于， 该纳米钻石烯的 C含量为 99〜100%。
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