CN103289017B - A kind of preparation method of multi-functional clay-based sand-fixation agent - Google Patents
A kind of preparation method of multi-functional clay-based sand-fixation agent Download PDFInfo
- Publication number
- CN103289017B CN103289017B CN201310259292.6A CN201310259292A CN103289017B CN 103289017 B CN103289017 B CN 103289017B CN 201310259292 A CN201310259292 A CN 201310259292A CN 103289017 B CN103289017 B CN 103289017B
- Authority
- CN
- China
- Prior art keywords
- sand
- clay
- fixation agent
- xanthan gum
- preparation
- 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
Landscapes
- Cultivation Of Plants (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a kind of preparation of clay-based sand-fixation agent, belong to technical field of defending and controlling sand.The present invention take clay as main raw material, and the sand-fixation agent that graft copolymerization acrylic amide, xanthan gum obtain, has nutrition, water conservation concurrently, the effects such as insulation, and has obvious promoter action to the growth of desert algae.Formed the natural condition of sand-fixing measure by simulation desert algae, sand-fixation agent can shorten the growth cycle of desert algae, is conducive to forming stable desert algae skinning fast on drift sand surface, reaches the object of administering drift sand fast; Meanwhile, the growth of desert algae can promote the formation of desert soil, for psammophyte provides nutrient, is biological and biological coordinate coexistence, promotes mutually.
Description
Technical field
The invention belongs to sand control sand prevention field
,relate to a kind of preparation of clay-based sand-fixation agent, particularly relate to a kind of preparation of the multi-functional clay-based sand-fixation agent that desert algae can be promoted to grow.
Background technology
China's desertification of land, desertification are very serious, and sand enters people and moves back situation still in the continuation of a lot of areas, and cause to environment for human survival and greatly destroy, preventing and fixing sand seems very necessary, urgent.Present stage, the major measure of preventing and fixing sand had engineering to fix the sand, chemical sand-fixing, sand consolidation with biologic and comprehensively to fix the sand.Engineering fixes the sand to refer to that thing of placing obstacles in desert or sandy land surface is husky or fix the sand object to stop stream to reach resistance.Chemical sand-fixing utilizes chemical material and technique exactly, by spraying chemical bond material on flowing sand ground, it is made to form at sandy land surface the protecting crust that one deck has some strength, separate the direct effect of air-flow to Shamian Island, improve the wind erosion-resistance performance of Shamian Island, the sand dune of commute generation sand damage or the construction of sandy earth's surface can prevent wind-force from blowing and raise and have the bonding course keeping moisture and improvement sand ground character, to reach control and to improve sand damage environment, and the object of raising sand ground productivity.Sand consolidation with biologic mainly comprises vegetative sand control and microorganism skinning fixes the sand.In numerous preventing and fixing sand measures, sand consolidation with biologic remains the most effectively, economy, environmental protection measure.But desert area rainfall is rare, and long-term quantity of precipitation is less than evaporation.Therefore in a sense, sand binding plant grows the decline that the moisture transpiration brought accelerates ground water table on the contrary.When ground water table drops to certain depth, sand binding plant also can be dead, as long as it is exactly inexorable trend that this situation does not change Desertification.By contrast, the miniature organism such as lichens, liver moss has obvious advantage.Its water requirement is extremely low, meta-bolites (exocellular polysaccharide) is bundled by the saccharan of mycelia, rhizoid or secretion, cohere the active bio skinning that soil, the grains of sand etc. form cushion, not only there is the effect of fixing Shamian Island, also can carry out photosynthesis, play the effect of solid carbon.Researcher finds, the skinning that lichens and liver moss algae etc. are formed is most important to desert soilization, and this desert soil has very important promoter action for the growth of psammophyte.
Summary of the invention
The object of the invention is for problems of the prior art, a kind of preparation method of the multi-functional clay-based sand-fixation agent that desert algae can be promoted to grow is provided.
One, the preparation of multi-functional clay-based sand-fixation agent
The preparation of the multi-functional clay-based sand-fixation agent of the present invention is under nitrogen protection, is dissolved in the water by xanthan gum and forms the solution of mass concentration 1 ~ 5%; Be warming up to 60 ~ 70 DEG C under stirring, constant temperature 0.5 ~ 1h, xanthan gum activated; Add initiator ammonium persulfate, be cooled to 40 ~ 55 DEG C after stirring 10 ~ 15min, add vinylformic acid, alkali, clay and linking agent N, N methylene-bisacrylamide; Continue to be warming up to 60 ~ 70 DEG C, isothermal reaction 2 ~ 3h; After reaction terminates, products therefrom is placed in air dry oven and is dried to constant weight, pulverizes, namely obtains multifunctional sand-fixation agent.
Described clay is loess or laterite;
Described xanthan gum is xanthan gum or guar gum;
The mass ratio of xanthan gum and clay is 1:1 ~ 1:6;
The mass ratio of described vinylformic acid and clay is 1:1 ~ 8:1;
The consumption of described ammonium persulphate is 1 ~ 4% of vinylformic acid quality;
Described alkali is NaOH, and alkali and acrylic acid mol ratio are 1:1 ~ 1:3;
The consumption of described linking agent N, N methylene-bisacrylamide is 0.2 ~ 0.6% of vinylformic acid quality.
Fig. 1 is the FT-IR spectrogram of clay, xanthan gum, xanthan gum grafted polyacrylic acid and xanthan gum grafted polyacrylic acid/clay.Wherein, a, b, c, d be respectively clay, xanthan gum, xanthan gum grafted polyacrylic acid, xanthan gum grafted polyacrylic acid/clay infrared spectrogram.Can find out, a curve is at 3616cm
-1the absorption peak at place is the stretching vibration peak of clay surface-OH, 1631cm
-1the absorption peak at place is the flexural vibration peak of-OH, and these absorption peaks disappear after polymerization substantially, 1029cm
-1the strong absorption peak at place is in clay=stretching vibration peak of Si-O, obviously weakens after polymerization, but still can observe in the spectrogram of xanthan gum-g-polyacrylic acid/clay.B curve is 1017,1073 and 1154cm
-1the absorption peak at place is the stretching vibration peak of C-OH, and these absorption peaks obviously weaken after polymerization, 1639cm
-1the absorption peak at place is the flexural vibration peak of-OH, substantially disappears after polymerization.C, d curve is all 1406,1452 and 1560cm
-1place's appearance-COO
-symmetrical stretching vibration peak and asymmetric stretching vibration peak.D curve is at 469cm
-1the Weak Absorption peak that place occurs is Si-O flexural vibration peak (because the content of clay is lower).Illustrate thus, clay and guar gum, vinylformic acid take part in graft copolymerization jointly, and defining with GG is the super absorbent resin of main skeleton.
Two,
the performance of clay-based sand-fixation agent
1, the test of water-absorbent and water-retentivity
Water-absorbent: take 0.05g(m
1) dry sample in the beaker of 500ml, add 250ml distilled water, after placing 3h, reach swelling equilibrium.Swell gel is leached with 50 order mesh screens and leaves standstill 10min elimination excessive moisture.Then quality (the m of swollen sample is weighed up
2), replicate(determination) is averaged for 3 times, is calculated as follows the water absorbent rate Qeq (g/g) of clay-based sand-fixation agent.
Qeq=(m
2-m
1)/m
1
Test result: the water absorbent rate of this clay-based sand-fixation agent is 400 ~ 630(g/g).
Water-retentivity: accurately take the fully swelling gel sample of 50g and be laid in 250ml beaker bottom, respectively room temperature, at 45 and 60 DEG C (being placed in baking oven) place, weigh the quality of a swollen sample every 1h.Be calculated as follows the water retention W of super absorbent resin
r.
W
R=W
i/W
o
W in formula
ofor the quality of complete swelling sample, W
ifor the quality of swollen sample in certain time interval.
Test result: this clay-based sand-fixation agent is at ambient temperature through 6d, and its water retention still has 28%, can water conservation 15h 45 DEG C time, also can reach 9h, show good Water-saving effect 60 DEG C time.Therefore, clay-based sand-fixation agent prepared by the present invention has excellent water-absorbent and water-retentivity, to the water supply that desert algae plant provides.
2, viscosity
Testing method: leached by fully swelling clay-based sand-fixation agent 50 order mesh screens, leaves standstill 15min, transfers in thick oral examination pipe, stirs and fully swelling clay-based sand-fixation agent is uniformly dispersed, and uses NDJ-8S Digital Viscometer to measure.
Test result: viscosity is at 2 ~ 8 (PaS), and therefore, clay-based sand-fixation agent prepared by the present invention has higher viscosity, and the ability of preventing and fixing sand is stronger.
3, heat-insulating property
Testing method: a certain amount of sand-fixation agent is made into 10%(mass ratio) aqueous solution, be sprayed at uniformly, sand bed surface, formed 1cm thick fix the sand tie layer, test fixes the sand to tie the temperature of different depths under layer.
Test result is shown in Fig. 2.As can be seen from Figure 2 fix the sand to tie layer and have good heat insulation effect.When Shamian Island temperature is 46 DEG C, lay thick the fixing the sand of 1cm and tie layer, after 6 hours, under fixing the sand to tie layer, different depths temperature tends towards stability, and change is significantly less than the temperature variation not having to lay and fix the sand to tie layer.
4, trophic analysis
Kjeldahl apparatus and atomic absorption instrument etc. is adopted to analyze sand-fixation agent nutritive ingredient.Partial Elements amount content is respectively: N:0.5-1.5%, K:1.1-3.2%, Ca:2.0-5.6%, Fe:1.5-2.8%, Mg0.3-0.7%.
Three, clay-based sand-fixation agent promotion that desert algae is grown
The microbial layer of earth's surface, Tengger desert edge thickness 2 ~ 10mm got by shovel, and removing impurity, pulverizes, and selects 1mm sub-sieve to sieve and gets skinning fragment as breeding parent.The sand getting Tengger desert is propagation substrate, makes breeding container with wooden seedling basin.The degree of depth of breeding container is at more than 50mm, and husky thickness is lower than container about 10mm.
Splendid attire sand in two breeding containers, husky thickness is lower than container about 10mm.Clay-based sand-fixation agent prepared by the present invention and the mass ratio of breeding masterbatch according to 1:1, and with 0.1kg/m
2amount uniform spreading be sprinkled upon surface husky in a wherein breeding container, even spray water, makes its surface fully moistening; And surface husky in another container, with 0.1kg/m
2amount uniform spreading spill breeding parent, even spray water, make its surface fully moistening.Suitably shade, temperature controls at about 30 DEG C.Observe algal grown situation: spill in the container of clay-based sand-fixation agent paving, 3 ~ 5 days there is growth sign in algae; About 10 days, algal grown amount reached peak value (amount of algae reaches maximum); About 15 days, sand bed surface formed the thick Algae preparation of 2 ~ 6mm; And do not having paving to spill in the container of clay-based sand-fixation agent, obviously do not observe the change examining algal grown.As can be seen here, the growth of clay-based sand-fixation agent to desert algae that prepared by the present invention has obvious promoter action.
In sum, the present invention take clay as main raw material, and the sand-fixation agent that graft copolymerization acrylic amide, xanthan gum obtain, has nutrition, water conservation concurrently, the effects such as insulation, and has obvious promoter action to the growth of desert algae.Formed the natural condition of sand-fixing measure by simulation desert algae, sand-fixation agent enough can shorten the growth cycle of desert algae, is conducive to forming stable desert algae skinning fast on drift sand surface, reaches the object of administering drift sand fast; Meanwhile, the growth of desert algae can promote the formation of desert soil, for psammophyte provides nutrient, is biological and biological coordinate coexistence, promotes mutually.
Accompanying drawing explanation
Fig. 1 is the FT-IR figure of clay, xanthan gum, xanthan gum grafted polyacrylic acid and xanthan gum grafted polyacrylic acid/clay;
Fig. 2 is for fixing the sand knot layer heat-insulating property (husky surface temperature 46 DEG C).
Embodiment
Be further described below by the preparation and property of specific embodiment to clay-based sand-fixation agent of the present invention.
Embodiment 1
1g guar gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.1g, after 10min, be cooled to 40 DEG C, then drip the N of 7.2g vinylformic acid, 2g sodium hydroxide, 3g loess, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 540g/g; Viscosity: 2.9PaS.
Embodiment 2
1g guar gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.12g, after 10min, be cooled to 40 DEG C, then drip the N of 7.2g vinylformic acid, 2g sodium hydroxide, 3g loess, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 510g/g; Viscosity: 5.4PaS.
Embodiment 3
1g guar gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.12g, after 10min, be cooled to 40 DEG C, then drip the N of 7.2g vinylformic acid, 2g sodium hydroxide, 1g loess, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 590g/g; Viscosity: 4.3PaS.
Embodiment 4
1g guar gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.12g, after 10min, be cooled to 40 DEG C, then drip the N of 7.2g vinylformic acid, 2g sodium hydroxide, 5g loess, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 450g/g; Viscosity: 6.4PaS.
Embodiment 5
0.5g xanthan gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.12g, after 10min, be cooled to 40 DEG C, then drip the N of 7.2g vinylformic acid, 2g sodium hydroxide, 3g laterite, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 435g/g; Viscosity: 3.7PaS.
Embodiment 5
2g xanthan gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.12g, after 10min, be cooled to 40 DEG C, then drip the N of 7.2g vinylformic acid, 2g sodium hydroxide, 3g laterite, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 426g/g; Viscosity: 7.1PaS.
Embodiment 6
1g xanthan gum is dissolved in the distilled water of 40mL and make solution, be under agitation warming up to 70 DEG C, constant temperature 1 hour; Drip the aqueous solution of the ammonium persulphate (APS) of 0.12g, after 10min, be cooled to 40 DEG C, then drip the N of 9g vinylformic acid, 2g sodium hydroxide, 3g laterite, 0.02g, N methylene-bisacrylamide (MBA) solution; Dropwise and be slowly warming up to 70 DEG C, isothermal reaction 3 hours afterwards; After reaction terminates, products therefrom is dried to constant weight as in air dry oven, pulverizes, obtain clay-based sand-fixation agent.Whole process is carried out under nitrogen protection.The water absorbent rate of clay-based sand-fixation agent: 608g/g; Viscosity: 5.8PaS.
Claims (4)
1. the preparation method of multi-functional clay-based sand-fixation agent, is under nitrogen protection, is dissolved in the water by xanthan gum and forms the solution of mass concentration 1 ~ 5%; Be warming up to 60 ~ 70 DEG C under stirring, constant temperature 0.5 ~ 1h, xanthan gum is activated; Add initiator ammonium persulfate, be cooled to 40 ~ 55 DEG C after stirring 10 ~ 15min, add vinylformic acid, alkali, clay and linking agent N, N methylene-bisacrylamide; Continue to be warming up to 60 ~ 70 DEG C, isothermal reaction 2 ~ 3h; After reaction terminates, products therefrom is placed in air dry oven and is dried to constant weight, pulverizes, namely obtains multifunctional sand-fixation agent;
Described clay is loess or laterite; Described xanthan gum is xanthan gum or melon glue; The mass ratio of xanthan gum and clay is 1:1 ~ 1:6; The mass ratio of vinylformic acid and clay is 1:1 ~ 8:1.
2. the preparation method of multi-functional clay-based sand-fixation agent as claimed in claim 1, is characterized in that: the consumption of described ammonium persulphate is 1 ~ 4% of vinylformic acid quality.
3. the preparation method of multi-functional clay-based sand-fixation agent as claimed in claim 1, it is characterized in that: described alkali is NaOH, alkali and acrylic acid mol ratio are 1:1 ~ 1:3.
4. the preparation method of multi-functional clay-based sand-fixation agent as claimed in claim 1, is characterized in that: the consumption of described linking agent N, N methylene-bisacrylamide is 0.2 ~ 0.6% of vinylformic acid quality.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310259292.6A CN103289017B (en) | 2013-06-26 | 2013-06-26 | A kind of preparation method of multi-functional clay-based sand-fixation agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310259292.6A CN103289017B (en) | 2013-06-26 | 2013-06-26 | A kind of preparation method of multi-functional clay-based sand-fixation agent |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103289017A CN103289017A (en) | 2013-09-11 |
CN103289017B true CN103289017B (en) | 2016-04-13 |
Family
ID=49090590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310259292.6A Active CN103289017B (en) | 2013-06-26 | 2013-06-26 | A kind of preparation method of multi-functional clay-based sand-fixation agent |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103289017B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103623787B (en) * | 2013-11-15 | 2016-08-24 | 西北师范大学 | The preparation of acrylic acid/polyvinylpyrrolidone/Paligorskite composite adsorbing material |
CN106638339B (en) * | 2017-01-18 | 2022-04-08 | 甘肃省治沙研究所 | Algae blanket and preparation method thereof |
CN108384556B (en) * | 2018-04-09 | 2021-07-02 | 孙美玲 | Preparation method of degradable sand fixing agent |
CN108865164A (en) * | 2018-08-21 | 2018-11-23 | 西北师范大学 | A kind of preparation method of inorganic clay-biogum composite water conservation material |
CN109722249A (en) * | 2018-12-27 | 2019-05-07 | 陶玲 | A kind of preparation method of desert algae type concave convex rod based high molecular sand fixation material |
CN110330980B (en) * | 2019-07-12 | 2021-07-23 | 浙江尚瑞特科技股份有限公司 | Degradable self-repairing water-retaining sand-fixing agent and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101186676A (en) * | 2007-11-13 | 2008-05-28 | 陕西科技大学 | Method for preparing water-loss reducer from xanthan gum radiation grafting PAA |
CN102617807A (en) * | 2012-03-23 | 2012-08-01 | 西北师范大学 | Preparation method of salt resistant composite water retention material |
-
2013
- 2013-06-26 CN CN201310259292.6A patent/CN103289017B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101186676A (en) * | 2007-11-13 | 2008-05-28 | 陕西科技大学 | Method for preparing water-loss reducer from xanthan gum radiation grafting PAA |
CN102617807A (en) * | 2012-03-23 | 2012-08-01 | 西北师范大学 | Preparation method of salt resistant composite water retention material |
Also Published As
Publication number | Publication date |
---|---|
CN103289017A (en) | 2013-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103289017B (en) | A kind of preparation method of multi-functional clay-based sand-fixation agent | |
CN106947492B (en) | A kind of composite sand consolidation model and its preparation method and application | |
CN103651072B (en) | Promote the special plant nutrient matrix of plant growing | |
CN104845640B (en) | The clay-based sand fixation material for function of being fixed the sand with water saving temperature adjustment | |
CN108865170A (en) | A kind of charcoal base soil structure conditioner preparation method and method of administration | |
CN101743790B (en) | Soil water ecological effectiveness control method | |
CN108570993B (en) | Ecological vegetation concrete slope protection structure and construction method thereof | |
CN103693909B (en) | Adopt the special plant cover concrete of slope protection greening of polymer aggregate technology | |
CN108949183A (en) | Desert greening method | |
CN104944892B (en) | A kind of eco-concrete for greening side slope and preparation method thereof | |
CN106279499B (en) | A kind of mineral compound water retaining agent and preparation method thereof | |
CN107466828A (en) | Ecologic planting plate and preparation method and application | |
CN107012098A (en) | A kind of preparation method of loess desert algae composite sand consolidation material | |
CN112390660B (en) | Special vegetation concrete for slope protection and greening and preparation method thereof | |
CN107384411A (en) | Modifying agent for prone soil | |
CN108048095A (en) | A kind of environmentally friendly water-retaining sand-stabilizing agent and preparation method and applications | |
CN107473647A (en) | A kind of ecological foam concrete for roof plant cultivation and preparation method thereof | |
CN111955309A (en) | Artificial sponge matrix for slope ecological restoration and construction method | |
CN106941802B (en) | A kind of ecologic sand control method | |
CN108951597A (en) | A kind of vegetative sand control method | |
CN108929703A (en) | A kind of preparation method of desert original position microorganism coating layer | |
CN112681343A (en) | Polymer spray-seeding auxiliary material for slope ecological restoration, spray-seeding material and construction method | |
CN104719114B (en) | Tomato soilless culture nutrient solution with fly ash aggregate as matrix | |
CN106810360A (en) | Afforesting matrix that a kind of protection against erosion is lost in and preparation method thereof and purposes | |
CN102150489B (en) | Method for quickly improving water-stable aggregate of sandy soil |
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 |