CN109957796A - 太阳能选择性吸收WC-Co复合涂层的制备方法 - Google Patents
太阳能选择性吸收WC-Co复合涂层的制备方法 Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 229910009043 WC-Co Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 title description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- 239000007921 spray Substances 0.000 claims abstract description 17
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000010288 cold spraying Methods 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 8
- 238000007788 roughening Methods 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 abstract description 4
- 230000002745 absorbent Effects 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 8
- 239000011195 cermet Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C23C18/125—Process of deposition of the inorganic material
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Abstract
本发明公开了一种太阳能选择性吸收WC‑Co复合涂层的制备方法，包括如下步骤：S1、将纳米结构的WC‑Co金属陶瓷粉末通过冷喷涂制备技术获得纳米结构WC‑Co金属陶瓷涂层，其中，WC陶瓷相颗粒大小控制在100nm～200nm，Co的质量分数在20%～30%之间，WC‑Co冷喷涂层厚度控制在50μm～150μm；S2、在上述WC‑Co金属陶瓷涂层表面采用溶胶‑凝胶法制备Al2O3减反层，Al2O3减反层厚度控制在10μm～50μm。本发明可实现相结构和成分移植，有利于控制粒子间结合，提高层间结合，所制备的复合涂层吸收性能良好，特别适用于工业应用推广。
Description
技术领域
本发明涉及复合涂层领域，具体涉及一种太阳能选择性吸收WC-Co复合涂层的制备方法。
背景技术
目前太阳能选择性吸收涂层大多数适用于中低温领域，当温度较高时，涂层将会发生吸收率下降、高温氧化、开裂剥落等现象，最终导致涂层光学性能衰减，因此合理选择涂层材料，采用合适的制备技术制备结构优良的涂层尤其必要。金属-电介质（金属陶瓷）选择性吸收涂层具有结构简单、高温条件下性能稳定、发射率较低等优点，特别适用于太阳能中高温领域的研究。WC-Co涂层是以WC作为陶瓷相，Co过渡金属为粘结相的金属陶瓷，该种金属陶瓷材料将具有潜在光谱选择特性的WC高熔点、良好的物相稳定性(500℃)和抗热震性与过渡族Co金属的良好吸收性及抗氧化性能相结合，有利于提高涂层的光吸收及高温热稳定性。然而，微米结构的WC-Co涂层因表面具有较大的表面粗糙度而使得涂层的光学吸收性能降低，传统的热喷涂技术因高温作用使得喷涂粒子存在分解、相变或氧化行为，以及热喷涂层中热应力较大，从而导致因涂层结构变化引起的吸收率、反射率及热稳定性能明显下降。纳米结构的晶粒尺寸效应可使涂层获得较高的品质因子及良好的热稳定性能。
目前采用的制备技术主要为涂料法、电镀法、电化学法、气相沉积法(PVD, CVD)、磁控溅射法及热喷涂法。涂料法工艺方法和操作简单，将色素材料与粘结剂制成的涂料涂敷在机体上可获得一定的性能涂料涂层，但涂料涂层发射率较大，涂层与基体之间结合较弱，有机粘结剂高温下会产生热分解现象，从而影响涂层的性能与使用寿命。电镀法制备的涂层光学性较好，但涂层的热稳定性和耐蚀性较差，同时镀液对环境会造成污染。电化学法可制备光吸收性能及热稳定性良好的涂层，但该技术投资大，成本高，制备流程较长。气相沉积法可获得具有良好光学性和耐热性的涂层材料，但工艺和操作复杂，投资成本大。磁控溅射法制备的金属陶瓷涂层具有良好的性能，但经过高温退火时，涂层表面会发生相变、开裂及脱落现象，从而导致涂层吸收性能下降。热喷涂法是制备金属陶瓷涂层最为常用的制备技术，但喷涂粒子在喷涂过程中由于高温作用在涂层中易出现杂相或相变现象，尤其不适用于制备纳米结构金属陶瓷涂层，对于沉积纳米WC-Co 涂层存在因碳化物分解产生的W2C、W或三元脆性相，难以实现以纳米WC 硬质颗粒移植至金属Co基体中而提高涂层光学吸收和热稳定性能的效果。
发明内容
为解决上述问题，本发明提供了一种操作工艺简单、成本较低的太阳能选择性吸收WC-Co复合涂层的制备方法，可实现相结构和成分移植，有利于控制粒子间结合，提高层间结合，所制备的复合涂层吸收性能良好，特别适用于工业应用推广。
为实现上述目的，本发明采取的技术方案为：
一种太阳能选择性吸收WC-Co复合涂层的制备方法，包括如下步骤：
S1、将纳米结构的WC-Co金属陶瓷粉末通过冷喷涂制备技术获得纳米结构WC-Co金属陶瓷涂层，其中，WC陶瓷相颗粒大小控制在100nm～200nm，Co的质量分数在20%～30%之间；
S2、在上述WC-Co金属陶瓷涂层表面采用溶胶-凝胶法制备Al2O3减反层，其中溶胶-凝胶法制备Al2O3减反层。所用的化学试剂为：异丙醇铝(分析纯≥99.8%)、丙三醇(分析纯≥99.7%)、浓硝酸(65%-68%浓度)、丙酮(分析纯≥99.7%)和去离子水等。
进一步地，基体材料为纯Al板，喷涂前需对基体材料进行喷砂粗化预处理。
进一步地，所述步骤S1中，喷涂送粉量为100g/min ～150g/min，WC-Co冷喷涂层厚度控制在50μm～150μm。
进一步地，所述步骤S2中，Al2O3减反层厚度控制在10μm ～50μm。
本发明具有以下有益效果：
1）通过冷喷涂技术可以将纳米结构WC-Co金属陶瓷粉末的组织结构原位移植至涂层中，同时可抑制纳米晶粒长大及避免由于高温作用导致出现分解或相变现象。
2）将具有潜在光谱选择特性的WC高熔点、良好的物相稳定性和抗热震性与过渡族Co金属的良好吸收性及抗氧化性能相结合，可提高WC-Co金属陶瓷涂层的光吸收及高温热稳定性。
3）纳米结构WC-Co金属陶瓷中的纳米晶粒尺寸效应可使涂层获得较高的品质因子及良好的热稳定性能。
4）在纳米结构WC-Co金属陶瓷涂层表面采用溶胶-凝胶法沉积获得Al2O3减反层形成复合涂层，可提高涂层的吸收性能。
附图说明
图1为WC-Co金属陶瓷冷喷涂层与粉末XRD图谱。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
原始喷涂粉末选用Co质量分数为20%的纳米结构WC-20Co金属陶瓷粉末，其中金属陶瓷粉末粒径为5μm-30μm，WC陶瓷颗粒尺寸为100nm -200nm；选用纯Al板作为喷涂基体，喷涂前对基体进行喷砂粗化处理；首先采用冷喷涂系统在Al基体表面沉积厚度为100μm左右的WC-20Co金属陶瓷涂层，喷涂气体采用N2，加速气体压力1.8MPa，送粉气压力2.0MPa，喷涂温度550℃，喷涂距离10mm，喷枪移动速度为50mm/s；然后在WC-20Co金属陶瓷涂层表面采用溶胶-凝胶技术沉积获得Al2O3减反层，Al2O3涂层厚度50μm，最终形成纳米结构的WC-20Co/Al2O3复合涂层。经X射线衍射分析表明，WC-20Co涂层的相结构和组织结构与原始喷涂粉末相同，Al2O3减反层的物相结构均为Al2O3相。WC-20Co/Al2O3复合涂层结合强度高，光学吸收及高温热稳定性能良好。
实施例2
原始喷涂粉末选用Co质量分数为23%的纳米结构WC-23Co金属陶瓷粉末，其中金属陶瓷粉末粒径为5μm-30μm，WC陶瓷颗粒尺寸为100nm-200nm；选用纯Al板作为喷涂基体，喷涂前对基体进行喷砂粗化处理；首先采用冷喷涂系统在Al基体表面沉积厚度为100μm左右的WC-23Co金属陶瓷涂层，喷涂气体采用N2，加速气体压力2.0MPa，送粉气压力2.2MPa，喷涂温度450℃，喷涂距离10mm，喷枪移动速度为100mm/s；然后在WC-23Co金属陶瓷涂层表面采用溶胶-凝胶技术沉积获得Al2O3减反层，Al2O3涂层厚度50μm，最终形成纳米结构的WC-23Co/Al2O3复合涂层。经X射线衍射分析表明，WC-23Co涂层的相结构和组织结构与原始喷涂粉末相同，Al2O3减反层的物相结构均为Al2O3相。WC-23Co/Al2O3复合涂层结合强度高，光学吸收及高温热稳定性能良好。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变化或修改，这并不影响本发明的实质内容。在不冲突的情况下，本申请的实施例和实施例中的特征可以任意相互组合。
Claims (4)
1.一种太阳能选择性吸收WC-Co复合涂层的制备方法，其特征在于：包括如下步骤：
S1、将纳米结构的WC-Co金属陶瓷粉末通过冷喷涂制备技术获得纳米结构WC-Co金属陶瓷涂层，其中，WC陶瓷相颗粒大小控制在100nm～200nm，Co的质量分数在20%～30%之间；
S2、在上述WC-Co金属陶瓷涂层表面采用溶胶-凝胶法制备Al2O3减反层,其中溶胶-凝胶法制备Al2O3减反层。
2.如权利要求1所述的太阳能选择性吸收WC-Co复合涂层的制备方法，其特征在于：基体材料为纯Al板，喷涂前需对基体材料进行喷砂粗化预处理。
3.如权利要求1所述的太阳能选择性吸收WC-Co复合涂层的制备方法，其特征在于：所述步骤S1中，喷涂送粉量为100g/min ～150g/min，WC-Co冷喷涂层厚度控制在50μm～150μm。
4.如权利要求1所述的太阳能选择性吸收WC-Co复合涂层的制备方法，其特征在于：所述步骤S2中，Al2O3减反层厚度控制在10μm ～50μm。
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