CN1060702C - Ionization radiation chemistry redox preparation method for nm metal powder - Google Patents
Ionization radiation chemistry redox preparation method for nm metal powder Download PDFInfo
- Publication number
- CN1060702C CN1060702C CN95100344A CN95100344A CN1060702C CN 1060702 C CN1060702 C CN 1060702C CN 95100344 A CN95100344 A CN 95100344A CN 95100344 A CN95100344 A CN 95100344A CN 1060702 C CN1060702 C CN 1060702C
- Authority
- CN
- China
- Prior art keywords
- metal
- solution
- radiation
- product
- alcohol
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a radiation chemistry preparation method for nanometer metal micro powder, which comprises the following steps: an optimized surfactant, an oxidation free radical scavenger and/or a metal ion chelating agent are added to the water solution of metal salt, metal halide or metal complex with proper concentration, and the solution is adjusted to a proper pH value; after deoxidization, the solution is irradiated by proper radiation dose in an ionization radiation field; a product is extracted and washed, and then, the nanometer metal micro powder is obtained after a drying process. The radiation chemistry preparation method for nanometer metal micro powder can carry out preparation under normal temperature and normal pressure and have the advantages of simple and feasible operating technology, narrow particle size distribution range of the product, uniform particle shape, high purity and high production rate, the average particle size is smaller than 100 nanometers, and the radiation chemistry preparation method is suitable for bulk production.
Description
The present invention relates to the nano level metal micro mist particularly noble metal, than the nano powder technology of preparing of active metal and LMP metal.
Usually the inert gas evaporation that adopts prepares nano material needs high vacuum and hot conditions, and output is few, is not suitable for producing in enormous quantities.Some scholar's research low concentration (10
-4M) the radiation chemistry effect of aqueous metal salt, for example Fu Jita human gamma-ray irradiations 10 such as (Fjita)
-4MHAuCl
4The aqueous solution obtains the colloidal solution that average grain diameter is the gold of 80nm, and paper publishing is on " nature " [Nature, 196,666 (1962)] of Britain.Because the ultrafine metal particle that radiationchemical reduction produces generally is scattered in the aqueous solution with colloidal state, need to handle again to obtain metal nano powder.For than active metal and low-melting-point metal, its oxidation-reduction potential has bigger negative value, and chemism is higher, and is therefore easily oxidized in preparation process, especially more unstable when they are in atom or elementide state, this causes very big difficulty with regard to the preparation of giving nanometer metal micropowder.
The present invention develops into the effective ways that prepare nanometer metal micropowder with the ionization radiation chemistry redox method, has successfully solved from big concentration (more than or equal to 10
-3M) method for preparing the metal nano micro mist in the slaine or the metal complex aqueous solution, this method be particularly suitable for producing noble metal, than the nano powder of active metal and low-melting-point metal.
The preparation method of this nanometer metal micropowder is characterized in that, is 10 to a kind of concentration
-3In the slaine of-1M or its complex solution, add at least a surfactant, at least a oxidative free radical scavenger, salting liquid for copper, nickel, cobalt, cadmium, tin also must add a kind of complexing of metal ion agent, solution is transferred to suitable pH value, and after carrying out the deoxygenation processing, place the ionizing radiation field, with 0.1-10
3The Gy/s radiation dose rate, irradiation total absorbed dose 5 * 10
2-1 * 10
5Gy separates, washing, drying at last.
This method specifically may further comprise the steps: 1. the preparation of the aqueous solution: the composition of the aqueous solution comprises:
1) a kind of water miscible slaine or metal complex (below be referred to as component A).Metal is any among Au, Ag, Pt, Pd, Cu, Ni, Co, Sn, Pb, the Cd; Salt can be all water-soluble salts or its complex compounds such as sulfate, nitrate, hydrochloride, acetate, halide; The concentration of metal ion is not less than 1 * 10
-3-M is generally 1 * 10
-3-1M, 1 * 10
-2-1 * 10
-1M is preferable.
2) at least a surfactant or deflocculant (below be referred to as B component).Can from polyvinyl alcohol, lauryl sodium sulfate, NaLS, dodecyl sodium sulfate, PVP and sodium polyphosphate, choose, its concentration below 1M, 1 * 10
-2-5 * 10
-2M is preferable.
3) scavenger of at least a water radiolytic product oxidative free radical (below be referred to as component C).Can choose from n-butanol, isopropyl alcohol, ethanol, propyl alcohol, gelatin, n-octyl alcohol, n-amyl alcohol or other alcohol, its concentration is below 10M, and 1-4M is better.
4), need to add complexing agent (below be referred to as component D) for the aqueous solution of copper, cobalt, nickel, cadmium, tin metal ion.For example EDTA or NH
3H
2O or alkali metal hydroxide, its concentration is below 10M.
2. solution is transferred to suitable pH value.
3. deoxygenation.Can feed inert gas or nitrogen or hydrogen in solution realizes.
4. solution is placed the ionising radiation field with suitable close rate irradiation a few hours to tens hour.In general, close rate can be at 0.1-10
3Choose in the scope of Gy/s.The radiation total absorbed dose is 5 * 10
2-1 * 10
5In the Gy scope.The ionized radiation source that uses comprises accelerated electron beam, alpha ray, β ray, gamma-rays and X ray.
5. the product in the solution behind the irradiation is separated.Described separation method comprises and at room temperature staticly settles filtration for a long time, or separates with centrifugal process, or method such as hydrothermal treatment consists.Separated products with distilled water and/or ammonia scrubbing for several times till the free from admixture.60-150 ℃ of drying, promptly obtain the metal nano micro mist at last.
This method prepares the metal nano micro mist, be to utilize the radiation chemistry redox of metal ion in the aqueous solution, its basic principle is a RADIATION DECOMPOSITION water and produce reductive free radicals such as aqueous electron, H atom, organic free radical therein, and these reproducibility grain kinds are metallic atom with the metal ion gradual deoxidizing:
Metallic atom is agglomerated into metal atomic cluster, forms the colloidal state aggregate again, and last nucleating growth becomes ultrafine metal particle.Because radiationchemical reduction is carried out in the aqueous solution step by step, and the static stabilization of surfactant is arranged, so the little and narrow distribution range of ultrafine metal particle particle diameter that generates.
Adopt the inventive method can prepare the nano level metal micro mist at normal temperatures and pressures, comprise torpescence metal A u, Pt, Pd, Ag and Cu, active metal Ni, Cd, Sn, Pb, Co, the products therefrom particle diameter is less, and generally at 5-40nm, maximum is no more than 100nm.The productive rate of product is higher; And no matter be torpescence metal or active metal, in air atmosphere, all the same stable with common corresponding metal.
Adopt the inventive method to prepare the nano level metal micro mist, the concentration of component A is unsuitable too small, is lower than 1 * 10
-3M often can not get micro mist, and can only obtain the colloidal metal particle.But if the concentration of component A is greater than 1M, then the particle diameter of the metal ultrafine powder of Huo Deing is difficult to assurance.The consumption of B component is relevant with the consumption of component A, and the A consumption can be used B less less, and the A consumption greatly then correspondingly needs to use B more.B is very few, and deficiency is so that colloidal solution is stable, and the carrying out of too much unfavorable redox reaction, and also uneconomical economically.The consumption of component C is 10-100 a times of A consumption, obtains removing to guarantee oxidative free radical 100% ground that generates in the water RADIATION DECOMPOSITION process.The consumption of component D and E is decided on the person's character of prepared metal ultrafine powder.
The size of particle diameter is limited by composition, concentration, pH value, total radiation dose, close rate and the treatment temperature of mixed aqueous solution.Radiation source, radiation dose rate and the total radiation dose that is fit to is decided by composition and concentration, irradiation atmosphere and the temperature of mixture in the aqueous solution and may influences the product productive rate and the other factors in ultra micro powder footpath.
Described hydrothermal treatment consists is meant the irradiation rear solution placed autoclave, and in 80-200 ℃ temperature range heated at constant temperature 1-10 hour, cooled and filtered was isolated product.
Describedly solution is transferred to suitable pH value be meant being controlled in the alkaline range than the salt of active metal or the pH value of its complex solution.For the salting liquid of metals such as nickel, cobalt, tin, cadmium, add buffering to or alkaline reagent, as NH
3H
2The O/ ammonium salt, NH
3H
2O or alkali metal hydroxide are to regulate its pH to desirable value.
Prepare nanometer metal micropowder with the inventive method and have following advantage:
1) particle of product metal ultrafine powder is little, is generally less than 100nm.
2) particle size distribution range of product metal ultrafine powder is narrow, and granular size is more even.
3) granular size of product metal ultrafine powder and shape can be controlled by regulating preparation condition, and the metallic particles that is generated under proper condition has the pattern of homogeneous.
4) the reduction of metal ion process can be carried out under room temperature (being generally in-5～50 ℃ of scopes) and normal pressure, the oxidation of metal or further growing up of particle under the hot conditions of having avoided must adopting with other method, the high temperature.
5) product purity is higher.
6) preparation technology is simple, and cost is lower.
7) productive rate is higher, is easy to produce in batches.
Below in conjunction with embodiment the present invention is done more specifically detailed explanation.
Embodiment 1. preparation nano-silver powders
To concentration is the AgNO of 0.05M
3Add a certain amount of C in the aqueous solution
12H
25NaSO
4Making its concentration is 0.1M, adds a certain amount of (CH again
3)
2It is 6.0M that CHOH makes its concentration.In solution, feed high-purity N
20.8 hour.The solution for preparing exists
60In Co γ-radiation field with 1.0 * 10
2The close rate irradiation of Gy/min 5 hours.105 ℃ of hydrothermal treatment consists 2 hours, collect product, with ammonia scrubbing product three times, use the distilled water washed product again three times earlier.Place baking oven,, promptly get the nanometer Ag powder in 80 ℃ of dryings 2 hours.Adopt the analyses of transmission electron microscope (TEM) and X-ray powder diffraction (XRD) to show that product A g powder average grain diameter is less than 15nm, the Ag particle is sphere.The productive rate of product A g powder can reach more than 95%, the radiation chemical yield G value (atom/100eV) can reach more than 10 of Ag.
Embodiment 2. preparation copper nanoparticles
Preparation contains 0.01M CuSO
4, 0.01M EDTA, 0.1M C
12H
25NaSO
4, 3.0M (CH
3)
2The aqueous solution of CHOH feeds high-purity N
21 hour.The solution for preparing exists
60In Co γ-radiation field with 3.6 * 10
4The absorbed dose of radiation irradiation of Gy was collected product in 2 hours 110 ℃ of hydrothermal treatment consists, used the distilled water washed product then each three times with ammoniacal liquor earlier, was drying to obtain nano Cu powder.TEM and XRD analysis show that product C u powder is that spheric granules is formed, and average grain diameter is less than 20nm, and the productive rate of copper powder can reach more than 70%.
Embodiment 3. preparation nanometer platinum powders
Preparation contains 0.001M H
2PtCl
6, 0.001M C
12H
25NaSO
4, 2.0M (CH
3)
2The aqueous solution of CHOH feeds high-purity N
20.5 hour deoxygenation.
60In the Co gamma radiation field with 1.8 * 10
3Gy absorbed dose of radiation irradiation.Staticly settle the collection product,, be drying to obtain nanometer Pt powder with distilled water washed product secondary.Tem analysis demonstration product P t powder is made up of spheric granules, and average grain diameter is less than 5nm.
Embodiment 4. preparation nano-nickel powders
Preparation contains 0.05M Ni (CH
3COO)
2, 0.4M NH
3H
2O or NH
3H
2O/ ammonium salt buffering is to, 0.01M C
12H
25NaSO
4, 2.0M (CH
3)
2The aqueous solution of CHOH fed high-purity Ar 1 hour in above-mentioned solution.The solution for preparing exists
60In Co γ-radiation field with 6.0 * 10
4The absorbed dose of radiation irradiation of Gy.Staticly settle the collection product,, be drying to obtain nanometer Ni powder earlier with the ammonia scrubbing secondary, use the distilled water washed product three times again.XRD analysis shows that product is by single-phase composition of metal Ni of face-centred cubic structure; TEM shows that its average grain diameter is less than 10nm.The optimum yields of Ni powder can reach more than 90%.Hot analysis result shows that product Ni powder can stable existence in the air atmosphere below 220 ℃.
Embodiment 5. preparation nanometer cadmium powder
Preparation contains 0.01M CdSO
4, 0.01M C
12H
25NaSO
4, 1.0MNH
3H
2O/ (NH
4)
2SO
4Buffering is to, 6.0M (CH
3)
2The aqueous solution of CHOH.In above-mentioned solution, feed high-purity H
21 hour.Then solution is placed on
60In Co γ-radiation field with 2.9 * 10
4Gy absorbed dose of radiation irradiation is with centrifugal process separated and collected product.With distilled water washed product three times, be drying to obtain nanometer Cd powder.Product is made up of spherical metal Cd particle, and average grain diameter is less than 30nm, and the productive rate of Cd powder can reach 30%.
Embodiment 6. preparation nanometer glass puttys
Preparation contains 0.01M SnCl
2, 0.5M NaOH, 2.0M (CH
3)
2The aqueous solution of CHOH.Adding NaOH in the present embodiment, is to make Sn in the solution
2+Ion is with HSnO
2 -Form exists and makes solution keep alkalescence.Feed high-purity N
21 hour.Above-mentioned solution is placed on
60In Co γ-radiation field, with 2.5 * 10
4Gy absorbed dose of radiation irradiation.Staticly settle the collection product, use distilled water washed product four times, be drying to obtain nanometer Sn powder.TEM and XRD analysis show that product is single-phase tetragonal metal Sn, is made up of spheric granules, and average grain diameter is less than 30nm.The productive rate of Sn powder can reach more than 40%.Heat analysis shows that product S n powder can stable existence in about air atmosphere below 200 ℃.
Some nano level metal micro mists and the character thereof prepared with chemical radiation of the present invention are listed in the following table.
Annotate: 1.T
m o(℃) initial melt temperature;
| Example | Product | Productive rate | Average grain diameter (nm) | Differential thermal analysis |
| Conversion ratio %G value | TEM method xrd method | T m o(℃) T oxi o(℃) | ||
| 1 | Ag | ＞95 9．6 | 15 13 | 944(952) |
| 2 | Cu | ＞70 | 20 16 | (1083) 160 |
| 3 | Pt | 5 5 | (1773．5) | |
| 4 | Ni | ＞90 4．4 | 10 8 | (1455) 220 |
| 5 | Cd | ～30 | 15 20 | (320．8) |
| 6 | Sn | ～40 | 30 | 220(231．89) |
| Other | Pb | 45 | (327) | |
| Pd | 10 | (1549．4) | ||
| Au | 10 | (1063) | ||
| Co | 22 | (1495) |
2.T
Oxi o(℃) initial oxidation temperature;
3. the interior data of bracket () are the fusion point of corresponding common polycrystalline metal.
Claims (8)
1. the preparation method of a nanometer metal micropowder is characterized in that, is 10 to a kind of concentration
-3In the slaine of-1M or its complex solution, add at least a surfactant, at least a oxidative free radical scavenger, salting liquid for copper, nickel, cobalt, cadmium, tin also must add a kind of complexing of metal ion agent, solution is transferred to suitable pH value, and after carrying out the deoxygenation processing, place the ionizing radiation field, with 0.1-10
3The Gy/s radiation dose rate, irradiation total absorbed dose 5 * 10
2-1 * 10
5Gy separates, washing, drying at last.
2. according to the method for claim 1, be characterised in that described ionized radiation source is alpha ray, β ray, gamma-rays, X ray or quickens electronics.
3. according to the method for claim 1, be characterised in that the metallic element in described slaine or its complex compound comprises gold, silver, copper, platinum, palladium, cobalt, nickel, cadmium, tin, lead.
4. according to the method for claim 1, be characterised in that described surfactant can be received from polyvinyl alcohol, lauryl sodium sulfate, lauryl sulfonic acid, choose the PVP, polyphosphoric acid sodium salt, be suitable for concentration 1 * 10
-2-1M.
5. according to the method for claim 1, be characterised in that described oxidative free radical scavenger can choose from n-butanol, different two alcohol, ethanol, propyl alcohol, gelatin, n-octyl alcohol and n-amyl alcohol or other alcohol, suitable concentration is 1-10M.
6. according to the method for claim 1, be characterised in that described complexing agent can choose from ammoniacal liquor, EDTA or alkali metal hydroxide, suitable concentration is 0.01-10M.
7. according to the method for claim 1, be characterised in that described suitable substance P H value is meant being controlled at alkaline range than the salt of active metal or the pH value of its complex solution.
8. according to the method for claim 1, be characterised in that the method for separating nanometer metal micropowder in the aqueous solution behind the described irradiation is hydrothermal treatment consists or staticly settles or centrifugation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95100344A CN1060702C (en) | 1995-01-16 | 1995-01-16 | Ionization radiation chemistry redox preparation method for nm metal powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95100344A CN1060702C (en) | 1995-01-16 | 1995-01-16 | Ionization radiation chemistry redox preparation method for nm metal powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127177A CN1127177A (en) | 1996-07-24 |
| CN1060702C true CN1060702C (en) | 2001-01-17 |
Family
ID=5073398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95100344A Expired - Fee Related CN1060702C (en) | 1995-01-16 | 1995-01-16 | Ionization radiation chemistry redox preparation method for nm metal powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060702C (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093023C (en) * | 1997-02-03 | 2002-10-23 | 中国科学技术大学 | Ultraviolet irradiation process preparing metal and metal oxide superfine powder and metal film |
| CN1058254C (en) * | 1997-11-03 | 2000-11-08 | 李道火 | Preparation of nanometer-level active composite powder |
| CN1074331C (en) * | 1998-03-03 | 2001-11-07 | 浙江大学 | Preparation of nanometer silver-copper alloy powder |
| CN1095411C (en) * | 1998-05-29 | 2002-12-04 | 中国科学院化学研究所 | Preparation of metal nanometre cluster |
| JP4636454B2 (en) | 2003-05-13 | 2011-02-23 | 三菱マテリアル株式会社 | Manufacturing method and use of metal nanorods |
| CN1322952C (en) * | 2004-09-24 | 2007-06-27 | 昆明贵金属研究所 | Indirecting light chemical preparation for gold nanometer material |
| KR100795987B1 (en) * | 2006-04-11 | 2008-01-21 | 삼성전기주식회사 | Method for Manufacturing Nickel Nano Particle |
| US7648556B2 (en) | 2006-04-11 | 2010-01-19 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing nickel nanoparticles |
| CN100464909C (en) * | 2007-03-29 | 2009-03-04 | 上海大学 | Method for making nana copper-tin alloy by electronic beam irridation |
| CN101684551B (en) * | 2008-09-27 | 2012-10-17 | 比亚迪股份有限公司 | Non-metallic component with metalized surface and manufacturing method thereof |
| CN101612671B (en) * | 2009-07-13 | 2011-04-27 | 浙江大学 | Method for preparing nanometer copper powder by using <60>Co-gamma rays in aqueous solution |
| CN102219189A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing hydrogen peroxide by adding hydrogen in anthraquinone |
| CN102240547B (en) * | 2010-05-14 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of carbon four selective hydrogenation catalyst and preparation method thereof |
| CN102069193B (en) * | 2011-01-17 | 2012-07-04 | 华东理工大学 | Method for preparing granularity-controllable narrow-distribution spherical easily-dispersible silver powder through radiation reduction |
| CN102773494A (en) * | 2011-05-13 | 2012-11-14 | 华东理工大学 | Method for preparing silver-coated copper powder through radiation reduction |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
| CN103008684A (en) * | 2013-01-21 | 2013-04-03 | 北京大学 | Method for preparing metal nanoparticles by means of atmospheric pressure cold plasmas |
| CN103464783A (en) * | 2013-09-18 | 2013-12-25 | 上海大学 | Method for preparing nano-dendritic platinum catalyst |
| CN105315963B (en) * | 2014-07-29 | 2017-07-21 | 北京市射线应用研究中心 | Electromagnetic shielding material and its nano composite material and their preparation method |
| CN105178021A (en) * | 2015-09-18 | 2015-12-23 | 浙江理工大学 | Preparation method of pure-cotton fabric easy to clean |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052071A (en) * | 1989-11-28 | 1991-06-12 | 中南工业大学 | From ammonium tungstate solution, produce the method for fine and ultrafine tungsten powder |
-
1995
- 1995-01-16 CN CN95100344A patent/CN1060702C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052071A (en) * | 1989-11-28 | 1991-06-12 | 中南工业大学 | From ammonium tungstate solution, produce the method for fine and ultrafine tungsten powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1127177A (en) | 1996-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1060702C (en) | Ionization radiation chemistry redox preparation method for nm metal powder | |
| Čubová et al. | Synthesis of inorganic nanoparticles by ionizing radiation–a review | |
| CN101451270B (en) | Method for large scale preparation of noble metal nano wire | |
| Temgire et al. | Optical and structural studies of silver nanoparticles | |
| Li et al. | Nanocrystalline silver particles: synthesis, agglomeration, and sputtering induced by electron beam | |
| EP0363552B1 (en) | Process for preparing metal particles | |
| EA010338B1 (en) | Stabilizing solutions for submicronic particles, methods for making the same and methods of stabilizing submicronic particles | |
| US8084140B2 (en) | Silver platelets comprising palladium | |
| CN1108214C (en) | Method for preparation of golden powder by decomposing aerosol | |
| CN108393501B (en) | Preparation method of Cu nanowire with controllable diameter | |
| US20110262646A1 (en) | Surfactant-Assisted Inorganic Nanoparticle Deposition on a Cellulose Nanocrystals | |
| CN1249276C (en) | Method for preparing stable nanometer cuprous oxide whiskers with chemical precipitation method | |
| JP2006089786A (en) | Method for producing metallic nano-particle dispersed in polar solvent | |
| WO2012017446A2 (en) | Improved process for the preparation of stable suspension of nano silver particles having antibacterial activity | |
| CN114425055B (en) | Silica supported multi-metal nano-particle, preparation method and antibacterial application thereof | |
| KR20180106753A (en) | Method for preparing transition metal nano particles and transition metal nano particles prepared by the same | |
| Qiao et al. | γ-Irradiation preparation and characterization of nanocrystalline ZnS | |
| CN112691689A (en) | Steam irradiation reduction synthesis method of monatomic catalyst | |
| CN112705724A (en) | Adjustable gold nanostructure and preparation method and application thereof | |
| CN111957986A (en) | Spherical nano copper powder and preparation method and application thereof | |
| Yang et al. | Metal-based composite nanomaterials | |
| CN1108858C (en) | Nanometer grade transtion metal and its alloy colloid and prepn. method thereof | |
| JP2006161102A (en) | Method for producing metal nanostructure | |
| CN1092605C (en) | Radiation synthetic preparing method for nanometer metal sulfide | |
| Kapoor et al. | Radiolytic production of metallic nanoclusters in a quaternary microemulsion system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |