纳米四氮化三硅 | 12033-89-5

• 物质功能分类: 无机化工 - 无机盐 - 氢化物、氮化物、叠氮化物
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 类金属有机物
• 中文名称: 纳米四氮化三硅
• 中文别名: 氮化硅粉末；纳米氮化硅；四氮化三硅；氮化硅；氮化硅(IV)
• 英文名称: silicon nitride
• 英文别名: silicon(IV) nitride；2,4,6,7-tetraza-1,3,5-trisilahexacyclo[3.1.1.01,4.02,5.03,6.03,7]heptane
• CAS: 12033-89-5
• 化学式: N₄Si₃
• 分子量: 140.283
• InChiKey: HQVNEWCFYHHQES-UHFFFAOYSA-N

物化性质

• 熔点：
  1900 °C
• 密度：
  3.44 g/mL at 25 °C (lit.)
• 物理描述：
  DryPowder
• 稳定性/保质期：
  由于它具有金刚石型三维晶格结构，因此具备高温热稳定性、抗热震性、化学稳定性和良好的电绝缘性及质硬性。易溶于氢氟酸，不溶于冷热水和稀酸，并且对浓硫酸和浓氢氧化钠溶液的作用也非常缓慢。 氮化硅存在α、β两种晶型。α-Si3N4为颗粒结晶体，而β-Si3N4则呈现针状晶体结构，两者都属于六方晶系，相对密度为3.18，莫氏硬度为9。它们具有较小的热膨胀系数和良好的化学稳定性，并且具有优良的抗氧化性。在约1900℃时分解为氮气和硅。氮化硅强度高且耐高温，在1200℃以上的高温下其强度不会改变，受热后不会熔成液体形态，直至达到1900℃才会开始分解。此外，它具有优异的耐化学腐蚀性能，能够抵抗几乎所有无机酸以及多种有机酸的侵蚀；氮化硅坚硬、热膨胀系数小，热震稳定性极好，绝缘性良好，化学性质稳定且机械强度高，不易氧化，可制成熔融铝、铅、镁、锡等金属的坩埚。

计算性质

• 辛醇/水分配系数(LogP)：
  -2.42
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• TSCA：
  Yes
• 危险品标志：
  Xi
• 安全说明：
  S22,S24/25
• 危险类别码：
  R37
• WGK Germany：
  3
• RTECS号：
  VW0650000

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
Product name : Silicon nitride
CAS-No. : 12033-89-5
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Not a hazardous substance or mixture according to Regulation (EC) No. 1272/2008.
Classification according to EU Directives 67/548/EEC or 1999/45/EC
Irritating to respiratory system.
Label elements
According to European Directive 67/548/EEC as amended.
Hazard symbol(s)
R-phrase(s)
R37 Irritating to respiratory system.
S-phrase(s)
S22 Do not breathe dust.
S24/25 Avoid contact with skin and eyes.
Other hazards - none

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substances
Formula : N4Si3
Molecular Weight : 140,28 g/mol
Component Concentration
Trisilicon tetranitride
CAS-No. 12033-89-5 -
EC-No. 234-796-8

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Section 4. FIRST AID MEASURES
Description of first aid measures
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration.
In case of skin contact
Wash off with soap and plenty of water.
In case of eye contact
Flush eyes with water as a precaution.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water.
Most important symptoms and effects, both acute and delayed
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.
Indication of any immediate medical attention and special treatment needed
no data available

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Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
nitrogen oxides (NOx), silicon oxides
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Avoid dust formation. Avoid breathing vapors, mist or gas.
Environmental precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
Sweep up and shovel. Keep in suitable, closed containers for disposal.
Reference to other sections
For disposal see section 13.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Provide appropriate exhaust ventilation at places where dust is formed.Normal measures for preventive fire
protection.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Specific end uses
no data available

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Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
General industrial hygiene practice.
Personal protective equipment
Eye/face protection
Use equipment for eye protection tested and approved under appropriate government standards
such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Choose body protection in relation to its type, to the concentration and amount of dangerous
substances, and to the specific work-place., The type of protective equipment must be selected
according to the concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
Respiratory protection is not required. Where protection from nuisance levels of dusts are desired,
use type N95 (US) or type P1 (EN 143) dust masks. Use respirators and components tested and
approved under appropriate government standards such as NIOSH (US) or CEN (EU).

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: powder
Colour: beige
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and no data available
boiling range
g) Flash point not applicable
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density 3,44 g/mL at 25 °C
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Autoignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
Other decomposition products - no data available

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Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation May be harmful if inhaled. May cause respiratory tract irritation.
Ingestion May be harmful if swallowed.
Skin May be harmful if absorbed through skin. May cause skin irritation.
Eyes May cause eye irritation.
Signs and Symptoms of Exposure
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.
Additional Information
RTECS: Not available

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Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
no data available

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Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company.
Contaminated packaging
Dispose of as unused product.

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Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA: no
Special precautions for user
no data available

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SECTION 15 - REGULATORY INFORMATION
N/A

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

氮化硅概述

氮化硅（Silicon Nitride）是一种具有高硬度、高温热稳定性及良好电绝缘性的陶瓷材料。其化学式为Si₃N₄，在工业上有广泛的应用。

性质与用途

• 物理性质：灰白色粉末状晶体，熔点1900℃，相对密度3.44。
• 化学稳定性：在空气中加热至1450～1550℃仍稳定，易溶于氢氟酸，不溶于冷热水及稀酸，并对浓硫酸和浓氢氧化钠溶液作用缓慢。

氮化硅主要用于制造超高温燃气透平、飞机引擎部件、热交换器等耐热材料，也可用作电炉的绝缘体或研磨工具。此外，在轴承、喷嘴以及特定条件下的专业窑具中也有广泛应用。

用途分类 超高温燃气透平与航空发动机

• 应用：主要作为超高温燃气透平叶片和飞机引擎部件，具有优异的热稳定性和机械强度。

机械设备中的高性能组件

• 轴承类：完全致密的氮化硅陶瓷能显著提高耐磨性、降低摩擦系数及增强刚度，特别适用于高温非润滑滚子和球轴承。
• 工业设备与工具：
  • 机床主轴 和 真空泵 使用混合型陶瓷轴承（通常由陶瓷球和钢圈构成）。
  • 电场探测器 及 潮汐流量计 等场合因海水侵蚀问题选择氮化硅材料，因其耐腐蚀性强。

制备方法

• 硅粉直接氮化法
• 二氧化硅还原法：该方法是目前工业上较为常用的方法。
  • 材料配比与工艺流程：
    • SiO₂(100份) + 炭黑(35份) + 尿素树脂(100份)
    • 水 (800份)，氧化铝 (0.1份)，草酸铵 (1份)，非离子表面活性剂 (0.3份)
  • 反应步骤：
    • 强搅拌并加入氨水调节pH值至9.0。
    • 喷雾干燥，然后在氮气环境中于1480℃下进行3小时氮化还原反应。
    • 再次脱碳处理后制得成品。

安全与应用挑战

• 毒性：β型碳化硅粉末的特性可参考相关安全标准。

尽管氮化硅具有诸多优越性能，但在大规模工业应用中仍面临成本高昂的问题。特别是在轴承制造领域，如何降低生产成本成为推广应用的关键难题之一。同时，在汽车非磨损组件、金属纯度控制、热电偶护套及熔融坩埚等方面也有广泛应用。

结语

随着技术的进步和新材料研发的不断深入，氮化硅在更多领域的应用潜力将得到进一步释放。未来的研究应侧重于降低成本的同时提高产品质量与性能，以满足更加广泛的实际需求。

反应信息

• 作为反应物：
  描述：

  金刚砂,耐火砂 、 纳米四氮化三硅 在 氮气 作用下， 反应 2.52h， 生成 Silicon Carbide Silicon Nitride
  参考文献：
  名称：

  FORMATION OF SILICON CARBIDE-SILICON NITRIDE NANOPARTICLE CARBON COMPOSITIONS

  摘要：

  一种具有碳质基体或硅基体纳米颗粒的组合物，该组合物不是粉末形式。一种具有硅和具有至少60％重量的焦炭产率或由有机化合物制成的热固性的组合物。一种将硅和有机化合物结合并加热形成碳化硅或氮化硅纳米颗粒的方法。

  公开号：

  US20130196844A1

文献信息

• Polymeric compositions and related methods of use
  申请人：Messersmith B. Phillip

  公开号：US20050288398A1

  公开（公告）日：2005-12-29

  Adhesive polymeric compositions which can comprise dihydroxyphenyl moieties and derivatives thereof, and related methods of use.

  粘合性聚合物组合物可以包括二羟基苯基基团及其衍生物，以及相关的使用方法。
• FORMATION OF SILICON CARBIDE-SILICON NITRIDE NANOPARTICLE CARBON COMPOSITIONS
  申请人：Keller Teddy M.

  公开号：US20130196844A1

  公开（公告）日：2013-08-01

  A composition having nanoparticles of silicon carbide and a carbonaceous matrix or silicon matrix. The composition is not in the form of a powder. A composition having silicon and an organic compound having a char yield of at least 60% by weight or a thermoset made from the organic compound. A method of combining silicon and the organic compound and heating to form silicon carbide or silicon nitride nanoparticles.

  一种具有碳质基体或硅基体纳米颗粒的组合物，该组合物不是粉末形式。一种具有硅和具有至少60％重量的焦炭产率或由有机化合物制成的热固性的组合物。一种将硅和有机化合物结合并加热形成碳化硅或氮化硅纳米颗粒的方法。
• Missing Member in the <i>M</i> ^II <i>M</i> ^III Si ₄ N ₇ Compound Class: Carbothermal Reduction and Nitridation Synthesis Reveal Substitution of Nitrogen by Carbon and Oxygen in CaLu[Si ₄ N _{7–2 <i>x</i>} C _<i>x</i> O _<i>x</i> ]:Eu ²⁺ /Ce ³⁺ ( <i>x</i> ≈0.3)
  作者：Lisa Gamperl、Otto E. O. Zeman、Philipp Strobel、Peter J. Schmidt、Wolfgang Schnick

  DOI：10.1002/chem.202104007

  日期：2022.1.19

  Carbon copy: The oxonitridocarbidosilicate CaLu[Si4N7–2xCxOx] (x≈0.3) has been synthesized by carbothermal reduction and nitridation. Incorporation of carbon was confirmed by 13C and 29Si MAS NMR spectroscopy. Complementary EDX measurements suggest that simultaneous incorporation of oxygen compensates for the negative charge excess induced by carbon. Eu2+- and Ce3-doped CaLu[Si4N7–2xCxOx] (x≈0.3) exhibit

  碳拷贝：通过碳热还原和氮化合成了氧氮化碳硅酸盐CaLu[Si 4 N 7–2 x C x O x ] ( x ≈0.3)。通过13 C和29 Si MAS NMR光谱证实碳的掺入。补充的 EDX 测量表明，同时掺入氧气补偿了由碳引起的负电荷过量。Eu 2+ - 和Ce 3-掺杂CaLu[Si 4 N 7–2 x C x O x ] ( x≈0.3) 分别表现出黄绿色和蓝色发射。
• Formation of silicon carbide-silicon nitride nanoparticle carbon compositions
  申请人：Keller Teddy M.

  公开号：US09045374B2

  公开（公告）日：2015-06-02

  A composition having nanoparticles of silicon carbide and a carbonaceous matrix or silicon matrix. The composition is not in the form of a powder. A composition having silicon and an organic compound having a char yield of at least 60% by weight or a thermoset made from the organic compound. A method of combining silicon and the organic compound and heating to form silicon carbide or silicon nitride nanoparticles.

  一种具有碳质或硅质基质的硅碳化物纳米颗粒组成的复合材料，该组成物不是粉末状的。一种具有硅和具有至少60%重量的焦炭产率或由有机化合物制成的热固性的组成物。一种将硅和有机化合物组合并加热以形成硅碳化物或硅氮化物纳米颗粒的方法。

表征谱图