CN109437917B - 一种两段还原氮化生产氮化钛及碳氮化钛的方法 - Google Patents
一种两段还原氮化生产氮化钛及碳氮化钛的方法 Download PDFInfo
- Publication number
- CN109437917B CN109437917B CN201811556519.2A CN201811556519A CN109437917B CN 109437917 B CN109437917 B CN 109437917B CN 201811556519 A CN201811556519 A CN 201811556519A CN 109437917 B CN109437917 B CN 109437917B
- Authority
- CN
- China
- Prior art keywords
- titanium
- carbon
- product
- stage reduction
- titanium nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 32
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005121 nitriding Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 229910009043 WC-Co Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- -1 As shown Chemical compound 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
- C04B35/58014—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
- C01B21/0765—Preparation by carboreductive nitridation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
- C04B35/58014—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON
- C04B35/58021—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON based on titanium carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Products (AREA)
Abstract
一种两段还原氮化生产氮化钛及碳氮化钛的方法。包括如下步骤：(1)配料：以二氧化钛和碳黑为原料混合搅拌均匀；(2)将步骤一所得的混合粉末放入高温炉中加热，在1300～1600℃、常压氩气环境下保温1～4小时，得到一段还原产物；(3)检测步骤二所得的一段还原产物碳含量及氧含量，根据所需产物与原料碳、氧、氮之间的关系调配碳量并球磨混合；(4将步骤三所得的混合粉末放入高温炉中，在1600～1800℃、常压氮气环境下保温2～8小时，冷却后得到氮化钛或碳氮化钛。本发明优点是：产品纯度高、粒度细且均匀、分散性好，且工艺流程简单，易于工业化生产；避免了生产过程中碳含量不易控制的缺点，产物中碳氮比例可控，生产出的氮化钛及碳氮化钛相单一，氧含量低，游离碳含量极低。
Description
技术领域
本发明属于金属陶瓷领域，具体涉及一种氮化钛及碳氮化钛的制备方法。
背景技术
近年来,由于碳氮化钛、氮化钛具有高熔点,高硬度,低摩擦磨损及耐腐蚀等特性,在制备金属陶瓷、切削工具、电极衬里材料、涂层材料等方面有较大的应用价值。尤其在切削刀具方面,碳氮化钛及氮化钛以其高硬度,高红硬性,高耐磨性及相对较低的密度成为了一种替代WC-Co硬质合金的潜在材料。在金属切削加工中,碳氮化钛、氮化钛基金属陶瓷刀具能抵抗切削瘤、起皮和陷穴的形成,在高速研磨粗加工、半加工工件的尺寸精度和加工表面质量都优于WC-Co硬质合金刀具所加工的工件。此外，由于氮化钛具有与黄金类似的光学性能，常用于仿金材料领域。因此，研发高纯度、细粒度、粒度均匀分散、物相单一的碳氮化钛、氮化钛粉末具有重大的价值。
国内外制备氮化钛的方法主要集中于直接氮化法和一步碳热还原氮化法。其中直接氮化为使用Ti或TiH2在含氮气氛下直接氮化，此方法优点是产物纯度高，产物粒度均匀，缺点是原料成本高。一步碳热还原氮化法为使用TiO2在氮气气氛下与碳质还原剂反应得到碳化钛，此方法优点是原料成本低，缺点是产物中存在的游离碳含量较高。此外，还有使用镁热还原氮化的方法，但该法制备出的产物粒度极不均匀，且生产过程涉及酸浸，对环境造成污染。
而制备碳氮化钛的方法主要集中于直接合金化法及碳热还原氮化法。其中直接合金化法直接使用TiC粉和TiN粉或Ti粉，球磨混合后在1700℃以上直接固溶得到。该法存在的问题在于，使用温度高，耗时长，能耗高，对设备要求高，产物颗粒大，且往往需要引入烧结助剂而导致产物纯度纯度下降。相较于直接合金化法，碳热还原氮化法具有原料成本低，工艺流程短，温度相对较低的优点。然而，由于目前碳热还原氮化法主要使用的一步反应合成，反应过程不可控，配碳量不准，造成了产物纯度低，粒度不均，产物C/N比例不可控且产物中存在多种碳氮化钛相等问题，尚未用于工业生产。部分研究者对此工艺进行了改进，如公开号为CN102718214A的专利所公开的方法是：采用控制氮气分压的方式来实现碳氮化钛中C/N比例可控的方法。但该法中仍存在反应产物气体中CO/CO2不可控，从而使配碳量难以控制的问题，多余的碳导致产物中含有大量游离碳，使得产物纯度降低。又如公开号为CN103193231A的专利所公开的方法是：通过浮选法去除产物中游离碳的目的。但该法存在碳氮化钛中C/N比例不可控的问题，同时由于采用的一段还原，产物中氧含量高，且得到产物的物相难以单一，易同时存在多种C/N比例的碳氮化钛。又如CN102976759A的专利所公开的方法是：先真空碳热还原再通氮气氮化的方法制备碳氮化钛。该法制得的产物氧含量低，但是需采用高温真空设备，对设备要求高，不易于工业化生产。又如CN108424147A的专利所公开的方法是：先低温真空还原后高温氮化的方法制备碳氮化钛，通过控制氮化时间来控制产物中C/N比例。该法能制备出氧含量低的碳氮化钛，但存在的问题主要有以下三点：1.需采用真空设备，不易于工业化生产；2.需采用快速降温装置，工业上实行有困难；3.采用在1300～1500℃控制氮化时间的方式来控制碳氮化钛中的C/N比，其原理是该温度下碳化钛能与氮气反应，虽然能生产碳氮化钛，但会有副产物单质碳产生，如
所示，且此反应在1600℃及之上温度会逆向反应，限制了氮化的温度，固溶过程将会很缓慢。
因此,研发一种工业可行,C/N比例可控,高纯度，窄粒度分布的碳氮化钛及氮化钛生产路径具有重要的意义。我们提出了两段还原氮化法生产碳氮化钛及氮化钛。本发明以二氧化钛和碳黑为原料，采用先在常压氩气氛围下通过碳热还原制备出TiCxOy前驱体,在定量配碳后，通过在常压氮气氛围下进行二段还原氮化，既能得到高纯度的碳氮化钛或氮化钛。该法的优势在于将难以控制配碳量的碳热还原反应分离出来作为第一段反应；而第二段氮化反应在低于1500℃时几乎不发生反应，只在高温区下进行，而此温度区气体产物只有CO生成，易于精准配碳，如
所示。因此，生成的产物TiCxOy通过测碳氧含量确定其x与y的值后，可以通过精准配碳的方式得到所需的产物。此外，本发明最低在1600℃下即能制备出低游离碳且物相单一的碳氮化钛或氮化钛产品。本发明在成本，流程和纯度等方面都具有明显的优势。
发明内容
本发明公开了一种两段还原氮化生产氮化钛及碳氮化钛的方法，本发明生产氮化钛及碳氮化钛包括如下步骤：
步骤一、配料：以二氧化钛和碳黑为原料，按照一定质量比混合搅拌均匀；
步骤二、一段还原：将步骤一所得的混合粉末放入高温炉中加热，在1300～1600℃、常压氩气环境下保温1～4小时，得到一段还原产物；
步骤三、定量配碳：检测步骤二所得的一段还原产物碳含量及氧含量，根据所需产物与原料碳、氧、氮之间的关系调配碳量并球磨混合；
步骤四、二段还原氮化：将步骤三所得的混合粉末放入高温炉中加热，在1600～1800℃、常压氮气环境下保温2～8小时，冷却后得到氧含量低,游离碳含量低,粒度细且均匀的氮化钛或碳氮化钛。
步骤一所述的二氧化钛、碳黑的摩尔比为1:1～3；步骤二所述的一段还原产物为TiCxOy，是一种碳化钛与一氧化钛所形成的固溶体；步骤四所制备出的氮化钛或碳氮化钛产物都为纯相且相单一，其中氧含量低于0.5wt％，粒径小于1微米，颗粒分散性好。
本发明的有益技术效果：
(1)采用二氧化钛和碳黑为原料，能制备出纯度高、粒度细且均匀、分散性好的氮化钛及碳氮化钛，且工艺流程简单，易于工业化生产；
(2)采用两段还原氮化的方法，相较于一步直接还原氮化的方法，避免了生产过程中碳含量不易控制的缺点，产物中碳氮比例可控，生产出的氮化钛及碳氮化钛相单一，氧含量低，游离碳含量极低。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合具体实施例，对本发明进行进一步详细描述。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。
相反，本发明涵盖任何由权利要求定义的在本发明的精髓和范围上做的替代、修改、等效方法以及方案。进一步，为了使公众对本发明有更好的了解，在下文对本发明的细节描述中，详尽描述了一些特定的细节部分。对本领域技术人员来说没有这些细节部分的描述也可以完全理解本发明。
实施例1
本发明以分析纯TiO2、炭黑(99.85wt％)为原料，按TiO2:C摩尔比为1:1.6的比例配料，然后利用研钵将配好的原料混合均匀；将混合后的原料放入高温炉内，在氩气流下以5℃/min的升温速率加热至1400℃，保温4小时，然后降至室温，得到TiCxOy前驱体，测得其碳含量为6.12wt％，氧含量为17.35wt％；以制备TiN为例，根据反应式
补碳6.90wt％，以200rpm球磨3小时混合均匀；将混合后的原料放入高温炉内，在氮气气流下以5℃/min的升温速率加热至1800℃，保温2小时，然后降至室温，得到碳含量约0.23wt％，氧含量约0.48wt％,氮含量约21.93wt％，粒径小于1μm的氮化钛产品。经X射线衍射(XRD)分析表明，产物物相为TiN，没有其他物相；电镜(SEM)表明，最终得到的TiN颗粒粒度均匀，分散性好。
实施例2
实施例2与实施例1基本相同，不同之处在于：
按TiO2:C摩尔比为1:2的比例配料，在氩气流下以5℃/min的升温速率加热至1500℃，保温1小时，然后降至室温，得到TiCxOy前驱体，测得其碳含量为10.48wt％，氧含量为11.90wt％；以制备TiC0.5N0.5为例，根据反应式
补碳8.16wt％，以400rpm球磨6小时混合均匀；将混合后的原料放入高温炉内，在氮气气流下以5℃/min的升温速率加热至1700℃，保温4小时，然后降至室温，得到碳含量约9.66wt％，氧含量约0.42wt％，氮含量约11.27wt％，粒径小于1μm的TiC0.5N0.5产品。经XRD分析表明，产物物相为TiC0.5N0.5，没有其他物相；SEM表明，最终得到的产物颗粒粒度均匀，分散性好。
实施例3
实施例3与实施例1基本相同，不同之处在于：
按TiO2:C摩尔比为1:1.8的比例配料，在氩气流下以5℃/min的升温速率加热至1600℃，保温4小时，然后降至室温，得到TiCxOy前驱体，测得其碳含量为8.48wt％，氧含量为14.40wt％；以制备TiC0.3N0.7为例，根据反应式
补碳8.11wt％，以300rpm球磨4小时混合均匀；将混合后的原料放入高温炉内，在氮气气流下以5℃/min的升温速率加热至1600℃，保温8小时，然后降至室温，得到碳含量约5.75wt％，氧含量约0.48wt％，氮含量约15.64wt％，粒径小于1μm的TiC0.3N0.7产品。经XRD分析表明，产物物相为TiC0.3N0.7，没有其他物相；SEM表明，最终得到的产物颗粒粒度均匀，分散性好。
实施例4
实施例4与实施例1基本相同，不同之处在于：
按TiO2:C摩尔比为1:1.8的比例配料，在氩气流下以5℃/min的升温速率加热至1600℃，保温4小时，然后降至室温，得到TiCxOy前驱体，测得其碳含量为8.48wt％，氧含量为14.40wt％；以制备TiC0.7N0.3为例，根据反应式
补碳15.83wt％，以300rpm球磨4小时混合均匀；将混合后的原料放入高温炉内，在氮气气流下以5℃/min的升温速率加热至1600℃，保温8小时，然后降至室温，得到碳含量约13.64wt％，氧含量约0.37wt％，氮含量约6.82wt％，粒径小于1μm的TiC0.7N0.3产品。经XRD分析表明，产物物相为TiC0.7N0.3，没有其他物相；SEM表明，最终得到的产物颗粒粒度均匀，分散性好。
Claims (2)
1.一种两段还原氮化生产氮化钛及碳氮化钛的方法，其特征在于：
步骤一、配料：以二氧化钛和碳黑为原料，按照一定摩尔比混合搅拌均匀；
步骤二、一段还原：将步骤一所得的混合粉末放入高温炉中加热，在1300～1600℃、常压氩气环境下保温1～4小时，得到一段还原产物；
步骤三、定量配碳：检测步骤二所得的一段还原产物碳含量及氧含量，根据所需产物与原料碳、氧、氮之间的关系调配碳量并球磨混合；
步骤四、二段还原氮化：将步骤三所得的混合粉末放入高温炉中加热，在1600～1800℃、常压氮气环境下保温2～8小时，冷却后得到氧含量低,游离碳含量低,粒度细且均匀且C/N比例可控的氮化钛或碳氮化钛；
步骤一所述的二氧化钛、碳黑的摩尔比为1:1～3；
步骤二所述的一段还原产物为TiCxOy，是一种碳化钛与一氧化钛所形成的固溶体。
2.如权利要求1所述的制备方法，其特征在于：步骤四所制备出的氮化钛或碳氮化钛产物都为纯相且相单一，其中氧含量低于0.5wt％，粒径小于1微米，颗粒分散性好。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811556519.2A CN109437917B (zh) | 2018-12-19 | 2018-12-19 | 一种两段还原氮化生产氮化钛及碳氮化钛的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811556519.2A CN109437917B (zh) | 2018-12-19 | 2018-12-19 | 一种两段还原氮化生产氮化钛及碳氮化钛的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109437917A CN109437917A (zh) | 2019-03-08 |
| CN109437917B true CN109437917B (zh) | 2020-06-12 |
Family
ID=65560091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811556519.2A Active CN109437917B (zh) | 2018-12-19 | 2018-12-19 | 一种两段还原氮化生产氮化钛及碳氮化钛的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109437917B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112357896B (zh) * | 2020-11-23 | 2022-05-27 | 株洲昊坤硬质材料有限公司 | 一种超细氮碳化钛的制备方法 |
| CN115093233A (zh) * | 2022-07-12 | 2022-09-23 | 吉林长玉特陶新材料技术股份有限公司 | 一种适合于工业化宏量生产的高纯超细过渡金属碳氮化物高熵陶瓷粉体的制备方法 |
| CN115385697B (zh) * | 2022-08-24 | 2023-06-23 | 湖南昊坤硬质新材料有限公司 | 一种高氮的氮碳化钛的生产工艺 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008069036A (ja) * | 2006-09-14 | 2008-03-27 | Yokohama National Univ | 導電性窒化ケイ素焼結体とその製造方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798234A (zh) * | 2010-02-12 | 2010-08-11 | 闫晓峰 | 一种碳氮化钛高炉护炉剂及其制备方法 |
| CN102976759A (zh) * | 2012-12-17 | 2013-03-20 | 长沙伟徽高科技新材料股份有限公司 | 一种真空还原氮化法制备碳氮化钛的方法 |
| CN103130506B (zh) * | 2013-03-15 | 2014-07-09 | 长沙伟徽高科技新材料股份有限公司 | 一种制备超细碳氮化钛的方法 |
-
2018
- 2018-12-19 CN CN201811556519.2A patent/CN109437917B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008069036A (ja) * | 2006-09-14 | 2008-03-27 | Yokohama National Univ | 導電性窒化ケイ素焼結体とその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109437917A (zh) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130506B (zh) | 一种制备超细碳氮化钛的方法 | |
| CN109437917B (zh) | 一种两段还原氮化生产氮化钛及碳氮化钛的方法 | |
| CN109576545B (zh) | 一种具有混晶结构的Ti(C,N)基金属陶瓷及其制备方法 | |
| CN108557783B (zh) | 高纯纳米氮化钛粉末的制备方法 | |
| CN115093233A (zh) | 一种适合于工业化宏量生产的高纯超细过渡金属碳氮化物高熵陶瓷粉体的制备方法 | |
| Wu et al. | Synthesis of tungsten carbide nanopowders by direct carbonization of tungsten oxide and carbon: Effects of tungsten oxide source on phase structure and morphology evolution | |
| KR101691410B1 (ko) | 탄질화티타늄 분말의 제조 방법 | |
| CN103924111A (zh) | 一种硬质合金纳米粒径粉末与高性能烧结块体材料的制备方法 | |
| Wang et al. | Preparation of high-purity and ultrafine WC-Co composite powder by a simple two-step process | |
| CN108080647B (zh) | 纳米/超细WC-Co复合粉末及其制备方法 | |
| Fan et al. | Synthesis of Ti (C, N, O) ceramic from rutile at low temperature by CH4-H2-N2 gas mixture | |
| CN100444997C (zh) | 一种简单快速的超细WC-Co复合粉的制备方法 | |
| CN102251130B (zh) | 一种超细晶粒硬质合金的制备方法 | |
| CN105154703B (zh) | 一种纯净单相三元碳化物Co6W6C的制备方法 | |
| Rui et al. | Preparation of high purity vanadium nitride by magnesiothermic reduction of V2O3 followed by nitriding in N2 atmosphere | |
| US20150064094A1 (en) | Method of preparing titanium carbide powder | |
| Wang et al. | A facile pathway to prepare ultrafine WC powder via a carbothermic pre-reduction followed by carbonization with CH4-H2 mixed gases | |
| CN109778046B (zh) | 一种低成本高性能混晶结构WC-Co硬质合金的制备方法 | |
| US11713251B2 (en) | Method for preparing powdered composite carbide of tungsten and titanium | |
| JPH0280318A (ja) | あらかじめ決められた粒子寸法を有する耐火性金属ホウ化物の合成法 | |
| CN108044126A (zh) | 利用废旧硬质合金制备板状结构WC-Co复合粉末的方法 | |
| CN112250080B (zh) | 一种两步制备难熔金属硼化物的方法 | |
| CN1385397A (zh) | 钛铁矿直接还原制备TiX(X=C、N)复合粉体的工艺方法 | |
| JPS6117403A (ja) | 金属硼化物、炭化物、窒化物、珪化物、酸化物系物質およびそれらの製造方法 | |
| Zhan et al. | Review on preparation of zirconium carbide and boride ceramic powders |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |