WO2022142124A1 - 一种基于Ca3TeO6结构的绿色颜料及其制备方法和应用 - Google Patents

一种基于Ca3TeO6结构的绿色颜料及其制备方法和应用 Download PDF

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WO2022142124A1
WO2022142124A1 PCT/CN2021/097637 CN2021097637W WO2022142124A1 WO 2022142124 A1 WO2022142124 A1 WO 2022142124A1 CN 2021097637 W CN2021097637 W CN 2021097637W WO 2022142124 A1 WO2022142124 A1 WO 2022142124A1
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green pigment
green
pigment
containing compound
preparation
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李满荣
周潇
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Sun Yat Sen University
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding or treatment with ultrasonic vibrations
    • C09C3/043—Drying, calcination
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/30—Camouflage paints
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/66—Hue (H*)

Definitions

  • the invention relates to the field of preparation of inorganic pigments, and more particularly, to a green pigment based on the structure of Ca 3 TeO 6 and a preparation method and application thereof.
  • Inorganic pigments are widely used in building materials, coatings and paints, plastics, inks, military camouflage and other industries because of their stable properties, bright colors, complete and pure varieties of chromatograms.
  • the existing commercial inorganic pigments still suffer from various problems.
  • traditional commercial pigments such as chrome yellow (PbCrO 3 ), cadmium yellow (CdS), antimony yellow (Sb 2 O 3 2PbO) and molybdenum chrome red [Pb(Cr, Mo, S)O 4 ] contain lead, Toxic heavy metal elements such as chromium and cadmium can harm human health and pollute the environment, and their application fields are also more and more restricted.
  • the pigment production process is complex and produces toxic by-products, which do not meet the requirements of energy conservation and environmental protection.
  • Chinese invention patent CN111978775A discloses (published on August 29, 2020) a military infrared reflective green inorganic pigment and its preparation method.
  • the inorganic pigment has good weather resistance, high temperature resistance, and light resistance, but its synthesis High temperature and acid and alkali resistance.
  • Chinese invention patent CN111154295A discloses (published on May 15, 2020) an environmentally friendly green inorganic pigment and its preparation method. The invention reduces the firing temperature of the pigment by adding highly active cobalt carbonate, but the invention describes Green pigments still have the problem of acid and alkali resistance.
  • the primary purpose of the present invention is to overcome the problems of poor acid and alkali resistance and high temperature resistance of green pigments in the prior art, and to provide a green pigment based on the Ca 3 TeO 6 structure, which is non-toxic, acid and alkali resistant, and high temperature resistant. .
  • Another object of the present invention is to provide the application of the above-mentioned green pigment.
  • a green pigment based on the structure of Ca 3 TeO 6 the molecular formula of the green inorganic pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.1 ⁇ x ⁇ 0.4.
  • the molecular formula of the green pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.2 ⁇ x ⁇ 0.3.
  • the element molar ratio Ca:Te:Mn:Li (3-2x):1:x:x, wherein 0.1 ⁇ x ⁇ 0.4.
  • the element molar ratio Ca:Te:Mn:Li (3-2x):1:x:x, wherein 0.2 ⁇ x ⁇ 0.3.
  • the calcium-containing compound is one or both of calcium carbonate and calcium oxide.
  • the manganese-containing compound is one or more of manganese carbonate, manganese monoxide, manganese dioxide and manganese trioxide.
  • the calcination is to raise the temperature to 900-1200°C at a heating rate of 4°C/min-10°C/min, and keep the temperature for 4-12 hours.
  • the green pigment of the invention is resistant to acid and alkali, high temperature, and has a reflectance value similar to that of green plants, and can be used for painting camouflage materials. Therefore, the application of the green pigment in the field of camouflage materials should also fall within the protection scope of the present invention.
  • FIG. 1 is the XRD pattern of the sample described in Example 1.
  • FIG. 1 is the XRD pattern of the sample described in Example 1.
  • Figure 2 is the appearance diagram of the sample before acid-base treatment (Sample) and after acid-base treatment described in Example 1.
  • the temperature was raised from room temperature to 900°C at a heating rate of 4°C/min, calcined in air for 12 hours, cooled down naturally, and a powder sample was obtained after taking out and grinding.
  • the powder samples are white because Li + ions are not introduced as activators, and Mn exists mainly in the divalent form.
  • the difference between the comparative example 2 and the embodiment 1 is that the calcination temperature in the comparative example 2 is 600°C.
  • Figure 1 is the XRD pattern of the sample described in Example 1. It can be seen from the figure that the phase of the sample described in Example 1 matches the XRD pattern of Ca 3 TeO 6 , indicating that the green pigment was successfully prepared in Example 1.
  • the XRD patterns of the samples described in Examples 2 to 5 are basically the same as those in Example 1.
  • the CIE (Commission on Illumination) standard 1976 is used to describe the color of pigments, that is, the perception of color stimuli and color quality received by the eye is converted into color coordinates L*, a*, b* representation.
  • the color coordinate values of the samples described in Examples 1 to 5 measured by a colorimeter and the calculated hue angle value h° are shown in Table 1.
  • Example 1 46.40 1.40 19.90 85.97
  • Example 2 55.23 0.64 22.62 88.38
  • Example 3 71.52 0.56 31.11 88.95
  • Example 4 30.76 0.63 9.67 86.27
  • Example 5 52.18 1.86 18.22 84.17
  • Examples 1 to 5 are close to the a* axis in the chromaticity space, and are biased towards the b* axis (yellow), and the hue angle values h° are 85.97°, 88.38, 88.95, 86.27, and 84.17, respectively. Because L* Lower values are visually green.
  • Example 1 The acid and alkali resistance test was carried out on the sample described in Example 1, that is, HNO 3 with a concentration of 5% and a NaOH solution with a concentration of 5% were prepared, and the pigment was added to the acid or alkali solution prepared above, and mixed and stirred for 10 minutes , filtered, washed with water and ethanol, and air-dried.
  • the sample described in Example 1 was subjected to a high temperature test, that is, the sample was calcined at a high temperature.
  • Figure 2 is the appearance diagram of the sample before acid-base treatment (Sample) and after acid-base treatment described in Example 1.
  • the color coordinate values of the samples before and after high temperature treatment and the calculated color difference ⁇ E * of the sample described in Example 1 are shown in Table 2.
  • the color difference ⁇ E * of the samples described in Examples 2 to 5 before and after high temperature treatment is the same as the Example 1 is basically the same.
  • Figure 3 is the XRD pattern of the sample described in Comparative Example 2. It can be seen from the figure that the phase of the sample does not match the XRD pattern of Ca 3 TeO 6 , that is, the green pigment cannot be prepared in Comparative Example 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

本发明公开了一种基于Ca3TeO6结构的绿色颜料及其制备方法和应用，所述绿色颜料的分子式为Ca3-2xMnxLixTeO6，其中0.1≤x≤0.4；所述绿色颜料的制备方法包括如下步骤：将原料含钙的化合物、含碲的化合物、含锰的化合物、Li2CO3按元素摩尔比称取后混合并研磨均匀在900～1200℃条件下煅烧，冷却后所得即为绿色颜料。本发明所述制备方法简单环保，原料平价且无毒性，制备得到的绿色颜料耐酸碱，1100℃以下颜料可保持颜色不变，且所述颜料反射率值与绿色植物的反射率相似，可用于伪装材料的涂装。

Description

一种基于Ca 3TeO 6结构的绿色颜料及其制备方法和应用 技术领域
本发明涉及无机颜料制备领域，更具体地，涉及一种基于Ca 3TeO 6结构的绿色颜料及其制备方法和应用。
背景技术
无机颜料因其性质稳定、色泽鲜艳、品种色谱齐全且纯正，而被广泛应用于建筑建材、涂料油漆，塑料、油墨、军事伪装等行业领域。然而，现有的商用无机颜料还存在各种各样的问题。其一，传统的商用颜料铬黄(PbCrO 3)、镉黄(CdS)、锑黄(Sb 2O 3·2PbO)和钼铬红[Pb(Cr,Mo,S)O 4]等含铅、铬、镉等有毒重金属元素，会危害人类健康和污染环境，其应用领域也受到越来越多的限制。其二，颜料生产过程复杂，并产生有毒副产物，不符合节能环保的要求。
中国发明专利CN111978775A公开了(公开时间2020年08月29日)一种军用红外反射绿色无机颜料及其制备方法，所述无机颜料具有很好的耐候性、耐高温性、耐光性，但其合成温度高且不耐酸碱。中国发明专利CN111154295A公开了(公开时间2020年05月15日)一种环保型绿色无机颜料及其制备方法，该发明通过添加活性高的碳酸钴降低了颜料的烧成温度，但该发明所述绿色颜料仍然存在不耐酸碱的问题。
发明内容
本发明的首要目的是克服现有技术中绿色颜料耐酸碱、耐高温性能差的问题，提供一种基于Ca 3TeO 6结构的绿色颜料，所述绿色颜料无毒、耐酸碱、耐高温。
本发明的进一步目的是提供上述绿色颜料的制备方法。
本发明的另一个目的是提供上述绿色颜料的应用。
本发明的上述目的通过以下技术方案实现：
一种基于Ca 3TeO 6结构的绿色颜料，所述绿色无机颜料的分子式为Ca 3-2xMn xLi xTeO 6，其中0.1≤x≤0.4。
基质Ca 3TeO 6为Mn离子提供了合适的配位环境，即CaO6，Ca和距离最近的6个O构成四棱双锥的八面体空间几何构型；TeO6，Te和距离最近的6个O 构成四棱双锥的八面体空间几何构型。Mn离子进入晶格后，占据Ca或Te的位置，在引入Li +之前体系中主要是二价Mn，Mn 2+在八面体中没有特殊的电子跃迁在可见区，即粉体不会有颜色。引入Li +后产生空穴，诱导体系中Mn的价态升高，此时体系中Mn的价态主要为四价，八面体配位环境中的Mn 4+在可见区产生特殊的跃迁使粉体颜色为绿色。
优选地，所述绿色颜料的分子式为Ca 3-2xMn xLi xTeO 6，其中0.2≤x≤0.3。
上述绿色颜料的制备方法，包括如下步骤：
将原料含钙的化合物、含碲的化合物、含锰的化合物、Li 2CO 3按元素摩尔比称取后混合并研磨均匀在900～1200℃条件下煅烧，冷却后所得即为绿色颜料。
优选地，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.1≤x≤0.4。
更优选地，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.2≤x≤0.3。
优选地，所述含钙的化合物为碳酸钙、氧化钙中的一种或两种。
优选地，所述含锰的化合物为碳酸锰、一氧化锰、二氧化锰和三氧化二锰中的一种或多种。
优选地，所述煅烧为以4℃/min～10℃/min的升温速率将温度升至900～1200℃，保温4～12h。
更优选地，所述煅烧为以4℃/min～6℃/min的升温速率将温度升至1000～1100℃，保温4～8h。
本发明所述绿色颜料耐酸碱、耐高温，且反射率值与绿色植物的反射率相似，可用于伪装材料的涂装。因此，所述绿色颜料在伪装材料领域中的应用也应该在本发明的保护范围内。
与现有技术相比，本发明的有益效果是：
本发明所述制备方法环保，原料平价且无毒性，制备得到的绿色无机颜料耐酸碱，1100℃以下颜料可保持颜色不变，且所述颜料反射率值与绿色植物的反射率相似，可用于伪装材料的涂装。
附图说明
图1为实施例1所述样品的XRD图。
图2为实施例1所述样品酸碱处理前(Sample)和酸碱处理后的外观图。
图3为对比例2所述样品的XRD图。
图4中(a)为实施例1所述样品的反射率光谱图，(b)为实施例3所述样 品的反射率光谱图，(c)为黄色叶片的反射率光谱图，(d)为绿色叶片的反射率光谱图。
具体实施方式
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。
实施例1
将原料CaCO 3，TeO 2，MnCO 3，Li 2CO 3按元素摩尔比Ca:Te:Mn:Li＝2.4：1：0.3：0.3称取后混合并研磨均匀放入马弗炉中，从室温以4℃/min的升温速率升温至1000℃，在空气中煅烧6小时，自然降温，取出研磨后即得到粉末样品。
实施例2
将原料CaO，TeO 2，MnO，Li 2CO 3按元素摩尔比Ca:Te:Mn:Li＝2.6：1：0.2：0.2称取后混合并研磨均匀放入马弗炉中，从室温以6℃/min的升温速率升温至1100℃，在空气中煅烧4小时，自然降温，取出研磨后即得到粉末样品。
实施例3
将原料CaCO 3，TeO 2，Mn 2O 3，Li 2CO 3按元素摩尔比Ca:Te:Mn:Li＝2.8：1：0.1：0.1称取后混合并研磨均匀放入马弗炉中，从室温以4℃/min的升温速率升温至900℃，在空气中煅烧12小时，自然降温，取出研磨后即得到粉末样品。
实施例4
将原料CaCO 3，TeO 2，MnO 2，Li 2CO 3按元素摩尔比Ca:Te:Mn:Li＝2.2：1：0.4：0.4称取后混合并研磨均匀放入马弗炉中，从室温以8℃/min的升温速率升温至1150℃，在空气中煅烧10小时，自然降温，取出研磨后即得到粉末样品。
实施例5
将原料CaCO 3，TeO 2，MnO 2，Li 2CO 3按元素摩尔比Ca:Te:Mn:Li＝2.4：1：0.3：0.3称取后混合并研磨均匀放入马弗炉中，从室温以10℃/min的升温速率升温至1200℃，在空气中煅烧8小时，自然降温，取出研磨后即得到粉末样品。
对比例1
将原料CaCO 3，TeO 2，MnCO 3按元素摩尔比Ca:Te:Mn＝2.4：1：0.3称取后混合并研磨均匀放入马弗炉中，从室温以4℃/min的升温速率升温至1000℃，在空气中煅烧6小时，自然降温，取出研磨后即得到粉末样品。粉末样品为白色，原因在于没有引入Li +离子作为激活剂，Mn主要以二价形式存在。
对比例2
本对比例2与实施例1的区别在于，本对比例2中煅烧温度为600℃。
对比例3
本对比例3与实施例1的区别在于，本对比例3中煅烧温度为1250℃。本对比例3未能制备绿色伪装颜料，原因在于1250℃条件下，样品褪色且部分融化。
表征
图1为实施例1所述样品的XRD图，从图中可以看出，实施例1所述样品的物相与Ca 3TeO 6的XRD图谱匹配，说明实施例1成功制备了绿色颜料。实施例2～5所述样品的XRD图与实施例1基本一致。
采用CIE(国际照明委员会)标准1976来描述颜料的颜色，即将眼睛接收到的颜色刺激和颜色质量的感知转换为颜色坐标L*、a*、b*表示。通过色度计测量的实施例1～5所述样品的颜色坐标值及计算得到的色相角度值h°如表1所示。
表1
  L * a * b * h°
实施例1 46.40 1.40 19.90 85.97
实施例2 55.23 0.64 22.62 88.38
实施例3 71.52 0.56 31.11 88.95
实施例4 30.76 0.63 9.67 86.27
实施例5 52.18 1.86 18.22 84.17
如表1所示，实施例1～5在色度空间中靠近a*轴，偏向b*轴(黄)，色相角度值h°分别为85.97°、88.38、88.95、86.27、84.17，由于L*值较低，视觉上为绿色。
对实施例1所述样品进行耐酸碱测试，即配置浓度为5％的HNO 3，浓度为5％的NaOH溶液，分别将颜料加入至上述配好的酸或碱溶液中，混合搅拌10分钟，过滤，再用水和乙醇洗涤，自然风干。另对实施例1所述样品进行高温测试，即将样品置于高温中煅烧。图2为实施例1所述样品酸碱处理前(Sample)和酸碱处理后的外观图，从图中可以看到，经过酸碱处理后，颜料颜色没有强烈变化，说明颜料耐酸碱。实施例2～5所述样品的酸碱测试结果与实施例1一致，酸碱及高温处理后颜色基本不变。
实施例1所述样品酸碱及高温处理前后样品的颜色坐标值及计算得到的色差ΔE *如表2所示，实施例2～5所述样品酸碱及高温处理前后样品的色差ΔE *与实施例1基本一致。
表2
  L * a* b* ΔE *
未处理 46.40 1.40 19.90 -
5％NaOH 46.03 1.56 19.41 0.63
5％HNO 3 47.10 1.35 19.68 0.73
1100℃ 46.98 1.67 19.75 0.66
从表2可看到，酸碱及高温处理后色差ΔE *小于1，进一步证明本发明所述颜料耐酸碱、耐高温。
图3为对比例2所述样品的XRD图，从图中可以看出，样品的物相与Ca 3TeO 6的XRD图谱不匹配，即对比例2未能制备得到所述绿色颜料。
图4中(a)为实施例1所述样品的反射率光谱图，(b)为实施例3所述样品的反射率光谱图，(c)为黄色叶片的反射率光谱图，(d)为绿色叶片的反射率光谱图，从图中可以看出，实施例1和实施例3所述样品在紫外-可见-近红外区(200-1200nm)内的反射率光谱与(黄色、绿色)树叶的反射率光谱类似，表明本发明所述颜料可用于伪装材料的涂装。实施例2、实施例4和实施例5的紫外-可见-近红外区(200-1200nm)内的反射率光谱与实施例1基本一致。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进 等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种基于Ca 3TeO 6结构的绿色颜料，其特征在于，所述绿色颜料的分子式为Ca 3-2xMn xLi xTeO 6，其中0.1≤x≤0.4。
  2. 如权利要求1所述绿色颜料，其特征在于，所述绿色颜料的分子式为Ca 3-2xMn xLi xTeO 6，其中0.2≤x≤0.3。
  3. 如权利要求1或2所述绿色颜料的制备方法，其特征在于，包括如下步骤：
    将原料含钙的化合物、含碲的化合物、含锰的化合物、Li 2CO 3按元素摩尔比称取后混合并研磨均匀在900～1200℃条件下煅烧，冷却后所得即为绿色颜料。
  4. 如权利要求3所述绿色颜料的制备方法，其特征在于，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.1≤x≤0.4。
  5. 如权利要求4所述绿色颜料的制备方法，其特征在于，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.2≤x≤0.3。
  6. 如权利要求3所述绿色颜料的制备方法，其特征在于，所述含钙的化合物为碳酸钙、氧化钙中的一种或两种。
  7. 如权利要求3所述绿色颜料的制备方法，其特征在于，所述含锰的化合物为碳酸锰、一氧化锰、二氧化锰和三氧化二锰中的一种或多种。
  8. 如权利要求3所述绿色颜料的制备方法，其特征在于，所述煅烧为以4℃/min～10℃/min的升温速率将温度升至1000～1100℃，保温4～12h。
  9. 如权利要求8所述绿色颜料的制备方法，其特征在于，所述煅烧为以4℃/min～6℃/min的升温速率将温度升至1000～1100℃，保温4～8h。
  10. 权利要求1或2所述绿色颜料在伪装材料领域中的应用。
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