60 research outputs found
Hydroporus kraatzii Schaum 1868
No full text<i>Hydroporus kraatzii</i> Schaum, 1868 <p> <i>Hydroporus kraatzii</i> Schaum, 1868 in KRAATZ (1868: 384) (original description).</p> <p> <i>Hydroporus kraatzii</i> Schaum, 1868 in SCHAUM & KIESENWETTER (1868: 66), <b>syn. nov.</b> (objective junior synonym and primary homonym, preoccupied by <i>H. kraatzii</i> Schaum, 1868 in KRAATZ (1868: 384); synonymy personally communicated by A. N. Nilsson, Umeå, Sweden).</p> <p> <i>Hydroporus kraatzii</i> Schaum, 1868 in SCHAUM & KIESENWETTER (1868: 66): SHARP (1882: 481) – NILSSON & HOLMEN (1995: 67) – NILSSON (2009a: 146).</p> <p> <i>Hydroporus kraatzi</i> Kiesenwetter, 1868: GEMMINGER & HAROLD (1868: 435) (incorrect authorship, referring to <i>H. kraatzii</i> Schaum, 1868 in SCHAUM & KIESENWETTER (1868)).</p> <p> <i>Hydroporus kraatzi</i> Schaum, 1868: ZIMMERMANN (1919: 169, 1920: 88, 1931: 153). – SCHAEFLEIN (1971: 38).</p> <p> <i>Hydroporus hedwigi</i> Reitter, 1897: 45: ZIMMERMANN (1919: 169) (synonymy with <i>H. kraatzii</i>). – NILSSON (2007: 51).</p> <p> <i>Hydroporus hedwigae</i> Schenkling, 1917: 52 (unjustified emendation of <i>H. hedwigi</i> Reitter): NILSSON (2007: 51) (synonymy).</p> <p> <b>Type locality.</b> Poland, ‘ Glatzer Schneeberg’ [‘Schneeberg’ = ‘snow mountain’; this mountain is called Králický Sněžník in Czech and Śnieżnik Kłodzki in Polish]. The border between the Czech Republic and Poland runs exactly across the peak of the mountain. The co-ordinates of the ‘ Glatzer Schneeberg’ are given in Wikipedia (access January 2009) as 50.201N 16.849E. According to KRAATZ (1968: 384), Kraatz himself collected at least some specimens on the northern slope of the ‘Glatzer Schneeberg’. It is therefore more likely that the type locality is in Poland and not in the Czech Republic.</p> <p> <b>Type material.</b> LECTOTYPE (by present designation): J, a small rectangular dark blue label, ‘Type’ [hw Cl. Müller], ‘Glatzer Schneebg’ [hw Cl. Müller], ‘Type von Hydr. Kraatzi Schaum’ [red, hw?], ‘ Lectotype, Hydroporus kraatzii Schaum, 1868, des. H. Fery 2009 ’ [red, printed] (ZSM).</p> <p> <b>Notes on the type material.</b> According to HORN et al. (1990: 345) and SCHERER (1982: 60), at least parts of Schaum’s Hydroporinae came ‘via E. A. H. v. Kiesenwetter, via Cl. Müller’ to the ZSM in 1905. It is known from other Schaum’s types that at least some of them were provided with a small rectangular dark blue label and/or that Clemens Müller, owing to his knowledge about the origin of the specimens, added labels in his own handwriting (see FERY 1992a: 67, 1992b: 119, 1992c: 343, 351; FERY et al. 1996: 315; FERY & BRANCUCCI 1997: 247). Thus, I have no doubt that the designated lectotype is a (former) syntype of <i>H. kraatzii</i> Schaum, 1868.</p> <p> HORION (1941: 393) reported that ‘types’ should be stored in the Deutsches Entomologisches Institut (DEI). However, DÖBLER (1976) did not list any types of <i>H. kraatzii</i> in the collections of the DEI and I have not been able to find such specimens during several visits at that institute.</p> <p> The first publication of the name <i>Hydroporus kraatzii</i> (KRAATZ 1868: 384) cites the species as ‘ <i>Hydroporus Kraatzii</i> Schaum n. sp. in litt.’ Although the author of that work is Kraatz, the authorship of the taxon must be assigned to Schaum because he is cited as the author. In addition, the taxon was described by Schaum a second time in SCHAUM & KIESENWETTER (1868: 66) (compare Article 50.1.1 including the Example in ICZN 1999).</p>Published as part of <i>Fery, Hans, 2009, New species of the Hydroporus longulus-group from Iran, Armenia and Turkey with a synopsis of the group (Coleoptera: Dytiscidae), pp. 529-558 in Acta Entomologica Musei Nationalis Pragae 49 (2)</i> on pages 550-551, DOI: <a href="http://zenodo.org/record/5320178">10.5281/zenodo.5320178</a>
Gyrinus urinator Drapiez 1819
No full textGyrinus urinator Drapiez, 1819 Gyrinus urinator Drapiez, 1819: 42 was missing in the ‘ PalCat ’. It is a junior primary homonym of Gyrinus urinator Illiger, 1807: 299, and thus Drapiez’s name is permanently invalid. The identity of this taxon might be objected because the author did not mention the bronzed shiny longitudinal stripes on the elytra; however, the yellowish brown ventral surface together with the type locality (Piedmont, Italy) leave no doubt that the species Drapiez studied is in fact G. urinator Illiger. Thus, Drapiez’s name is not only a homonym but also a junior subjective synonym of Illiger’s name.Published as part of Fery, Hans & Hájek, Jiří, 2016, Nomenclatural notes on some Palaearctic Gyrinidae (Coleoptera), pp. 645-663 in Acta Entomologica Musei Nationalis Pragae 56 (2) on page 65
Agabus turcmenus Guignot 1957
No full textAgabus turcmenus Guignot, 1957 Agabus (Gaurodytes) turcmenus Guignot, 1957: 93. Agabus turcmenus Guignot; Nilsson 1990: 152, 1995: 60. – Hua 2002: 35. – Brancucci & Hendrich 2008: 52. – Fery & Šťastný 2010: 1019. Agabus (Acatodes) turcmenus Guignot; Nilsson 2000: 23. Type locality. Kyrgyzstan, "Naryn kol." Notes: The word "kol" (also "kul") means "lake" in the Middle Asian Turk languages ("gölü" in Turkish); "Naryn kol" most probably refers to the Issyk-kul which means "hot lake" (personal communication by O. Merkl, curator in the HNHM). The Issyk-kul has co-ordinates of ca. 42N 76E, the city Naryn is situated about 100 km SE of that lake (ca. 41.4N 76.0E). Lectotype (by present designation): ♂, "Turkestan, Almásy 1906" [printed], "Naryn kol." ["Naryn" printed, "kol." hw Almásy?], " Holotypus 1957 ♂, Agabus (Gaurodytes) turcmenus Guignot " [white label with red margin, hw? (not hw Guignot!); unauthorised curatorial designation of holotype], "Type" [red, printed], "F. Guignot det. 1956, Agabus (Gaurodytes) turcmenus n. sp., Type ♂ " [hw Guignot in large part], " Lectotype, Agabus turcmenus Guignot, 1957, Fery des. 2011" [red, printed] (HNHM). Notes: The lectotype lacks the left mesotarsus. It is a rather immature specimen which I have, nevertheless, designated as lectotype because (1) it fits best the description in Guignot (1957) and because (2) a label in Guignot's handwriting is mounted at the pin. Notes: In Guignot (1957: 94) is given "Turkestan: Naryn kol. (Almanj, 1906)"; "Almanj" must be correctly "Almásy" which is the name of the collector. Paralectotypes: 2 ♂♂, 2 ♀♀, each with three labels, first two same as in the lectotype, third label " Paratypus 1957, Agabus turcmenus Guignot " [white label with red margin, hw? (not hw Guignot!); unauthorised curatorial designation of paratypes]; all paralectotypes with the respective red label (HNHM). Notes: The author of this taxon did not determined a holotype in the original description. It is even not clear whether he has studied only a single male or more specimens (the given range of total length suggests more than one specimen). This is why I assume that the specimens stored in the HNHM must be treated as syntypes and that a lectotype can be designated (cf. Recommendation 73E in ICZN 1999: 80). The curator of the HNHM (O. Merkl) advised me to cross through all red margined type labels and turn them with their upper side downwards. Descriptive notes. Guignot's description (1957: 93) is not very helpful because the author uses only a few of those characters which are seen as essential today. The author tells us that the species belongs to the congener - group and that it can be "recognised at first sight by its general shape and the colour of the elytra" [my translation]. One important hint is that the species has a bifid median lobe. Furthermore is stated that the pronotum is black, but narrowly brownish bordered all around, and the TL is given as 9.5–10 mm. Study of the lecto- and paralectotypes reveals, however, that the range of the TL is 8.4–8.9 mm (lectotype 8.9 mm; MW: 4.2–4.4 mm) and that the lectotype and three paralectotypes are immature. The latter fact explains that the pronotum of these specimens is rather broadly yellowish margined. The single mature specimen (a male; see Fig. 11) has the yellow border of the pronotum rather narrow but distinct laterally, at anterior margin still narrower, and at the hind margin more or less perceptible only before the scutellum. I want to add that the discontinuity in outline between the pronotum and elytra is rather distinct and that the last abdominal ventrite is provided with rather strong rugae. A. turcmenus is rather similar to A. thomsoni, but deviates chiefly by the reddish brown border of the pronotum, stronger rugae on last abdominal ventrite (Fig. 13), and the shape of the median lobe which is figured here for the first time (Figs 12 and 37). The left paramere is given in Fig. 14. A more detailed description of this species shall be postponed until more material from Kyrgyzstan has been studied. Distribution. So far known only from Kyrgyzstan and China (Xinjiang; see Nilsson 1995: 60).Published as part of Fery, Hans, 2011, Agabus (Acatodes) puetzi sp. n., a new species of the confinis-group from the Qinghai-Tibet Plateau (Coleoptera, Dytiscidae, Agabini), pp. 37-54 in Zootaxa 3050 on pages 46-4
PROSEDUR ADMINISTRASI TABUNGAN SIMPEDES PADA PT. BANK RAKYAT INDONESIA (PERSERO) UNIT TEMPUREJO CABANG JEMBER
No full textPelaksanakan Prosedur Administrasi Tabungan SIMPEDES adalah sebagai berikut : a. Pengisian formulir Kartu Contoh Tanda Tangan (KCTT), Tanda Setoran (Model OPS-07), Slip Tanda Penarikan (Model TAB 02) harus tepat dan jelas_ Hal itu dimaksudkan untuk mempermudah verifikasi formulir yang sudah divalidasi komputer, khususnya untuk formulir Tanda Setoran dan Slip Penarikan pada saat tutup jam kas. b. Pengisian buku register diisi berdasarkan peraturan nomor rekening serta berdasarkan identitas nasabah, seperti yang telah ditetapkan oleh perusahaan yang bersangkutan. Hal tersebut berfungsi untuk mempermudah dalam kegiatan pengadministrasian buku register
Dyticus parvulus O. F. Muller 1776
No full textDyticus parvulus O.F. Müller, 1776: 73 The text in Müller's work is reproduced in Fig. 2. My translation of the Latin text is: " D. parvulus, pronotum black, anteriorly yellow; elytra with a shortened stria; legs brownish black." Müller's description fits almost all species of Hydroglyphus and Bidessus occurring not only in northern Europe. However, since Müller's work deals with Scandinavian species, these should be either Bidessus unistriatus, B. grossepunctatus, Hydroglyphus geminus or H. hamulatus (Gyllenhal, 1813) (see e.g. Nilsson & Holmen 1995). The type locality of parvulus is Norway and Denmark (see Nilsson & Hájek 2019b: 104). The identity of the taxon cannot be checked since an insect collection of O.F. Müller never did exist or is totally lost (Horn et al. 1990b: 273; Evenhuis 1997: 555; Nilsson & Petrov 2006: 161; see also Nilsson & Hájek 2019b where under all taxa of O.F. Müller is given " syntypes lost"). I know of about 90 works in which the name parvulus is used (in combination with several different generic names and authors). Only in 12 of these works is it used as a valid name with author O.F. Müller, one of them is Crotch (1872: 204) who gave Goeze's and Schrank's names as synonyms of parvulus. Heyden (1880: 54) was the first who included the name as valid in combination with the generic name Bidessus Sharp; additionally, he gave geminus as a junior synonym. Baudi (1889: 34) and Ádám (1996) are the last authors who treated Müller's name as valid. Otherwise the taxon is mostly treated as synonym of unistriatus (with authors Schrank, Goeze or others, in several cases also as "sensu" name). Thus, we have the problem that parvulus O.F. Müller is an available name (although a nomen dubium) and possibly a senior subjective synonym of unistriatus Goeze and also of unistriatus Schrank, and might be even a senior subjective synonym of Dytiscus geminus Fabricius, 1792. Since parvulus is an almost forgotten name, the use of this name instead of either Goeze's or Schrank's or Fabricius' name would considerably threaten the stability of the nomenclature. It would be easy to give the younger name precedence over the older name by application of Article 23.9 of the ICZN (1999) —if Ádám (1996: 18, 60) would not have used it as valid name. Special problems arise because he even designated it as type species of Bidessus Bedel, 1881 (see also Bousquet & Bouchard 2018). It must be also mentioned that Müller's name was already involved in another nomenclatural problem. Motschulsky (1853b: 77) published a new species from Alaska with the name Dytiscus parvulus. The homonymy was removed by J. Balfour-Browne who replaced Motschulsky's name with Dytiscus alaskanus J. Balfour-Browne, 1944: 356, both names being now objective synonyms.Published as part of Fery, Hans, 2019, Nomenclatural notes on some taxa of Bidessus Sharp and designation of a neotype (Coleoptera: Dytiscidae: Hydroporinae: Bidessini), pp. 579-589 in Zootaxa 4565 (4) on page 582, DOI: 10.11646/zootaxa.4565.4.11, http://zenodo.org/record/259128
Israiliyyat Dalam Tafsir Al Khathib Asy-Syarbini
No full textThis article aims to reveal various israiliyyat data contained in the interpretation of Tafsir as-Siraj al-Munir by Muhammad asy-Syarbini, then analyzed comparatively with the views of other commentators. Therefore, the method that the author uses in this study is a qualitative method, it aims to be able to find out what israiliyyat material that ash-Syarbini mentions in his interpretation, what steps are taken in mentioning it as well as his response related to these stories and his relationship with the commentators before his time related to the story of israiliyyat. From the results of this study, the author succeeded in mapping the information system of the story mentioned by the author of the commentary, the views of scholars regarding these stories and the attitude of the author of the interpretation in commenting on israiliyyat as well as the roots of the views of asy-Syarbini
NEW FORMS OF FOCAL PRISMS
No full textCh. Fery, Astrophys, J. 34:79 (1911)Author Institution: ConsultantUntil now the only single-element focal prism known was that of which was based on an analogy to the concave diffraction grating and suffered, like it, from astigmatism and other aberrations. It is now proposed to combine an off-axis section of an Amici spherical surface with a reflecting spherical surface concentric with the wave front, to form a single-element autocollimating prism. Other combinations of these two types of surfaces yield composite prisms or prism trains. These systems will be practically free of spherical and other aberrations for one wavelength. The advantages of the design are: a minimum number of reflecting and refracting surfaces, low aberrations considering the simplicity of the design, and adaptability for multiplepass operation. Prisms with a liquid section are particularly appropriate, since they can be compressed to correct them for any desired wavelength. Fields of specific applicability of the design will be discussed
Hygrotus (Coelambus) nubilus
No full text<i>Hygrotus</i> (<i>Coelambus</i>) <i>nubilus</i> (LECONTE, 1855) <p> <i>Hydroporus nubilus</i> LECONTE, 1855: 298 (orig. descr); CLARK 1862: 178.</p> <p> <i>Coelambus nubilus</i> (LECONTE, 1855); SHARP 1882: 401; FALL 1919: 15 (designation of lectotype).</p> <p> <i>Hygrotus nubilus</i> (LECONTE, 1855); BLACKWELDER 1944: 76 (new combination); WALLIS 1973:102; ANDERSON 1983: 189 (description); HILSENHOFF (1994: 283); LARSON et al. 2000: 178.</p> <p> <i>Hygrotus</i> (<i>Coelambus</i>) <i>nubilus</i> (LECONTE, 1855); NILSSON 2001: 208; 2015: 180 (catalogue)</p> <p>Type locality: USA, Wyoming,GoshenCo.,FortLaramie(ca. 42.21N 104.52W).</p> <p>Type material (not studied): male lectotype and single female paratype (" allotype ") stored in the Museum of Comparative Zoology, Harvard University, Cambridge, Massachusetts, USA (see ANDERSON 1983: 189).</p> <p> Material studied (material from Hawaii): 1, " Mauna Kea, Hawaii, Lake Waiau, 13,000 '" [printed], " 3970 M, 2.IX.1977 " [handwritten], " F.G. Howarth, Collector, Bishop" [printed], " Hygrotus cf. medialis LeConte, GAS ’04 [= G.A. Samuelson 2004]" [handwritten]; 1, same labels except the last one " Hygrotus sp., det. G.A. Samuelson ’04" [handwritten in part] (both specimens in coll. H. Fery). Further nine specimens with similar label texts in Bishop Museum, Hawaii. Lake Waiau has co-ordinates 19.811N 155.477W and is situated in an altitude of about 3970 m (<b>first record from Hawaii</b>).</p> <p> Additional material studied: 32 exs from localities in Arizona, Colorado, Iowa, Maryland, New York, Oklahoma, Texas, Wyoming (all USA). Two females have been studied from Mexico (Chihuahua State, 1 mi E Coyame; specimens in coll. H. Fery and coll. G. Challet). BLACKWELDER (1944: 76) beside " U.S.A. " included also " Mexico " in the distribution area, however, without providing any exact data. This is why we consider our data at least as <b>first "reliable" record</b> of <i>H. nubilus</i> from Mexico. Chihuahua State belongs formally to the Neotropical zoogeographical region (as defined in NILSSON 2001: 10 and 2015: 7), but is very close to the border with the USA and, thus, in a transitional zone between the Nearctic and Neotropical regions. Beside <i>Hygrotus</i> (<i>Coelambus</i>) <i>fraternus</i> (LECONTE, 1852), <i>H.</i> (<i>Coelambus</i>) <i>lutescens</i> (LECONTE, 1852), <i>H.</i> (<i>Coelambus</i>) <i>wardii</i> (CLARK, 1862) and <i>H.</i> (<i>Hygrotus</i>) <i>hydropicus</i> (LECONTE, 1852) this is the fifth species of the genus occurring in Mexico.</p> <p>Descriptive notes: The species belongs to ANDERSON’ s (1983: 184) species group VI. This author provides also a key to species of this group. We refrain from reproducing a detailed description of the species, but instead refer to the original description of LECONTE (1855: 298). Also in FALL (1919: 15), ANDERSON (1983: 189) and LARSON et al. (2000: 178) are given valuable descriptive details. The male genitalia are figured in ANDERSON (1983: 179, figs 26a,b) and LARSON et al. (2000: 178). A photo of the female gonocoxae is given in HILSENHOFF (1994: 280, fig. 8).</p> <p> Nevertheless, we provide a photo of the habitus (Fig. 2) and want to point on the parameres which in the genus are unique in shape (together with those of <i>H. femoratus</i> (FALL, 1901); cf. ANDERSON 1983: 179, figs 25 and 26). Also the female gonocoxae and gonocoxosterna have shapes which are very helpful for identification. This is why we give our own illustrations of the male and female genitalia in Figs 3-6.</p> <p> <i>Hygrotus femoratus</i> is extremely similar to <i>H. nubilus</i> (females of both are inseparable on morphological characters) and only two males and one female have ever been collected (see ANDERSON 1983: 188). This is why ANDERSON (l.c.) even suspected that both might be the same. The only difference can be found in the male tibiae and femora which have a normal shape in <i>H. nubilus</i>, but are deviating in <i>H. femoratus</i> (ANDERSON 1983: 180: "male femora with enlarged apical articulations, tibia pedunculate"; see also figs 38a,b on p. 185).</p> <p> Distribution According to ANDERSON (1983: 189; see also fig. 4 on p. 175) <i>Hygrotus nubilus</i> is a common species which is widely distributed in boreal America (USA and Canada) east of the Rocky Mountains (for names of USA states and Canadian provinces see ANDERSON 1983: 189). With the records given in the present paper the distribution area must be widened to northern Mexico and to Hawaii.</p> <p> Discussion: The finding of <i>H. nubilus</i> on the Hawaii Islands is very surprising. We have no doubt that the species must have been introduced to Hawaii, but have no evidence for how this may have happened. It is also not clear when the species has been introduced because it seems to be very rare and collecting activities before 1977 may simply have failed although the species was already present on Mauna Kea or anywhere else.</p> <p>In HÄNEL & JÄCH (2013: 275 ff) several possibilities are discussed for the introduction of alien species on the islands of the Tristan da Cunha Archipelago. Among these are any kinds of human activities, but also transport by birds is mentioned: "In considering the possible ways in which... invertebrates could be dispersed naturally, birds have been considered as favoured vehicles, especially young ones that still have downy patches, as these are prone to becoming contaminated with debris."</p> <p> On the internet we found the website of DENNY (2006) where more than twenty species of ducks, geese, and shorebirds are listed which migrate to Hawaii each winter (on the northern hemisphere). Among these is the Pacific golden plover (= Kōlea in Hawaiian; <i>Pluvialis fulva</i> (GMELIN, 1789)) which is known to fly regularly from Alaska to Hawaii and back. This bird has already been observed in California (which is west of the Rocky Mountains, while <i>H. nubilus</i> occurs only east of these mountains; see also COSTE & SALMON 1998). This shows that it cannot be excluded principally that birds are able to cover such an immense distance.</p> <p> Another candidate is Taverner’s goose (<i>Branta hutchinsii taverneri</i> DELACOUR, 1951) which has been reported from Kansas (where <i>H. nubilus</i> has been recorded from) as well as from Hawaii "...for all recent reports of extralimital Taverner’s Geese, those we have reviewed suggest that this subspecies does occur as a vagrant in Hawaii and east of the Rockies..." (MLODINOW et al. 2008: 352).</p>Published as part of <i>Fery, Hans & Challet, Gil, 2015, Hygrotus (Coelambus) nubilus (LECONTE, 1855) on Mauna Kea (Hawaii) - first record of the genus from the Pacific zoogeographical region (Coleoptera: Dytiscidae), pp. 1303-1309 in Linzer biologische Beiträge 47 (2)</i> on pages 1304-1308, DOI: <a href="http://zenodo.org/record/5191312">10.5281/zenodo.5191312</a>
IMPLEMENTASI ALGORITMA APRIORI UNTUK REKOMENDASI PROMO BARANG DI MASTER KOMPUTER
No full textAbstract
The Apriori Algorithm Association rule is a rule-based machine assessment method. Based on the concept of a strong rule, association rules are used to create regularity between products in transaction data on a larger scale recorded by the point of sale system. A big part of the problem with sales is how to promote their products. The problem faced by Master Computer is the difficulty of determining which hardware sales package products are in great demand by customers to produce a combination of several hardware items that will be sold and promoted by the Master Computer Store. In this study, the author wants to build a website-based promo recommendation system using the association method and a priori algorithm.
Keywords: Master Computer, Apriori Algorithm, Promotio
Synthesis and Characterization of Nanoporous Resin Particles for Water Purification
No full textThrough progressive industrialization and the relentless consumption of natural raw materials, man is exerting a negative influence on his habitat. In particular, water as the basis of life and almost all processes of our economy is contaminated by various pollutants due to excessive use and insufficient purification. Here, oxyanions, heavy metal ions and organic pollutants pose a high risk to aquatic habitats and ultimately to humans. Due to insufficient removal, they also contribute to the loss of non-renewable raw materials for industrial cycles. Due to a mostly low effect concentration and potential interactions with diverse living organisms, the removal of many contaminants is extremely important to avoid further altering existing ecosystems.
Adsorption represents an energy-efficient method of removal using adsorbents suitable for this purpose. Highly cross-linked resin polymers such as poly(melamine-co-formaldehyde) (PMF) with its excellent chemical resistance, high number of functional groups and ease of preparation, represent promising starting points for adsorbents.
This dissertation describes the colloidal aqueous synthesis of nanoporous resin particles (e.g. PMF) by templating with SiO2 nanoparticles (SiO2 NPs), which are subsequently used to adsorb water pollutants. An overall goal of this work consists of elucidating the mechanism for particle and pore formation by systematically varying various synthesis parameters. Electron microscopy, N2-soprtion and particle size measurement are used to analyze the morphology, size and pore structure of the particles. Comprehensive investigations thus allow to determine the influence of each tested synthesis parameter on these properties.
A very important goal, especially for future large-scale applicability, is the colloidal production of uniform particles, which have both a high ordered porosity and particle diameters in the range of a few micrometers. This enables an application as a fixed-bed adsorber that can be flowed through. This goal is closely linked to the mechanistic elucidation of pore and particle formation in the synthesis.
The prepared nanoporous PMF particles were tested for various adsorption applications after their characterization. In order to obtain a comprehensive picture of the applicability of PMF particles, experiments with oxyanions, with pharmaceuticals as representatives of organic pollutants and with heavy metal ions will be carried out respectively. On the one hand, these experiments will focus on investigating the adsorption performance and mechanism of PMF with the respective pollutant. On the other hand, the influence of the changed porosity on the adsorption mechanism is investigated by using different particles of a varied synthesis parameter.
Sulfate and phosphate ions were investigated in the oxyanion class. Extremely high separation rates were demonstrated for both ions, significantly outperforming previous commercially available materials. In experiments concerning a potential selective adsorption and thus separation of both species, the PMF/SiO2 hybrid particles, in which the template had not yet been removed, showed a selective sulfate adsorption.
The immobilization of heavy metal ions was analyzed with special focus on the simultaneous separation of the Cu2+ ions and respective anions used here. Investigations of the adsorbent after the adsorption experiments by means of electron microscopy, X-ray scattering and electron spin resonance spectroscopy elucidated the adsorption mechanism, which had been insufficiently analyzed so far. Here, adsorption and surface-induced precipitation were identified as partially separate subprocesses, both of which are responsible for the separation of both metal and anions from solution. In adsorption experiments with the monovalent ions nitrate and chloride, a two-step uptake process was identified, which was mathematically described for the first time via a new adsorption isotherm.
In the scope of organic water pollutants, the separation of the pharmaceutical diclofenac is being tested. In particular, the adsorption of pharmaceuticals is an urgent issue due to their low effect concentration and ubiquity in surface and tap waters. Pharmaceutical separation using PMF has hardly been investigated worldwide despite its promising properties. In these experiments, particles templated with SiO2 NPs of different sizes and stabilized in different ways were tested. This resulted in pore systems that varied from each other especially in their accessibility of the pore system and in the diameter of the connecting channels between the main cavities. These characteristics significantly affected the adsorption capacity and separation rates in low concentration range.
A final goal is to synthesize a resin network that uses an equally highly functional triazine-based monomer instead of melamine. The monomer 2,4,6-tris(2,4,6-trihydroxyphenyl)-1,3,5-triazine (3PT) possesses nine hydroxyl groups each, whereby a polymer based on it should exhibit strongly modified adsorption properties compared to PMF. This monomer was used in an aqueous polymerization analogous to PMF to produce a previously unknown polymer network, which was designated P(3PT-F). Here, templating was omitted because the newly prepared material already exhibited intrinsic nanoporosity due to the size of the 3PT monomer. In subsequent adsorption experiments, very high separation rates were demonstrated for the toxic metal ions Pb2+, Cd2+ and Ni2+. In realistic initial concentrations, the contamination was reduced to drinking water quality in each case. P(3PT-F) also showed highly selective removal of Pb2+ over the common ions Ca2+, Mg2+, K+ and Fe2+. As fundamental evidence, reusability was also demonstrated by complete desorption with dilute HCl and subsequent re-adsorption without significant reduction in capacity.
Overall, starting from the fundamental study of PMF particle synthesis, a more general understanding of aqueous dispersion polymerization of hydrophobic resins was first derived and templating with hydrophilic SiO2 NPs was implemented. With the help of understanding the particle growth processes and interactions responsible for templating, the properties of the resulting particles could be controlled. Subsequently, the influence of the changed porosity in particular on the separation performance could be investigated in the adsorption studies. In addition, it was possible to analyze which interactions PMF enters into with the respective pollutant types. By replacing the monomer melamine with a hydroxyl-containing monomer, a novel resin polymer could be produced. With its altered porosity and reactivity, this can now serve as a new starting point for adsorption experiments with strongly altered adsorption performance, e.g. towards heavy metal ions.:Abstract 1
Kurzfassung 5
List of Publications 9
First-Author Publications 9
Co-Author Publications 10
Patent 12
Conference Proceedings 12
Oral Presentations 12
Poster 12
List of Figures 13
Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 14
Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 15
Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 16
SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 18
Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 19
List of Tables 21
Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 21
Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 21
Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 22
SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 22
Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 23
Abbreviations 25
Symbols 26
1. Introduction 1
2. Objectives and Experimental Design 5
3. Scientific Background 11
3.1. Poly(melamine-co-formaldehyde) 11
3.1.1. Polymerization Mechanism 11
3.1.2. Synthesis Strategies for the Preparation of Porous PMF Particles. 13
3.1.3. Fields of Application of PMF 13
3.2. Adsorption 15
3.2.1. Adsorption Isotherms and Mathematical Modeling 16
3.3. Surface Precipitation 20
4. Fundamentals of Instrumental Analytics 23
4.1. Gas Sorption Measurements 23
4.1.1. Determination of Pore Sizes 26
4.1.2. Determination of Specific Surface Area 27
4.2. Transmission Electron Microscopy 29
4.3. Inductively Coupled Plasma Optical Emission Spectroscopy 31
Results and Discussion 33
Chapter Overview 33
5. Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal 37
Graphical Abstract 37
Abstract 37
1. Introduction 38
2. Results and Discussion 39
2.1. Synthesis and Characterization of the PMF Particles 40
2.2. Sorption Experiments 47
3. Materials and Methods 54
3.1. Materials 54
3.2. Methods 54
3.3. Synthesis of the PMF Particles 56
3.4. Water Treatment Experiments 57
4. Conclusions 59
6. Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal 65
Graphical Abstract 65
Abstract 65
1. Introduction 66
2. Materials 68
3. Methods 68
3.1. Synthesis of the PMF particles 70
3.2. Water treatment experiments with diclofenac solution 72
3.3. Theoretical model 72
3. Results and Discussion 73
3.1. Synthesis and characterization of the PMF particles 74
3.2. Adsorption of Pharmaceutics 80
4. Conclusion 84
7. Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles 89
Graphical Abstract 89
Abstract 89
1. Introduction 90
2. Materials and methods 91
2.1. Materials 91
2.2. Synthesis of the Poly(melamine-co-formaldehyde) particles 92
2.3. Methods 93
2.4. Water treatment experiments 96
3. Results and discussion 97
3.1. Synthesis and characterization of the PMF particles 98
3.2. Cu2+ uptake experiments 102
3.3. Mechanism for Cu2+ and Anion Removal 115
3.4. Investigation of other heavy metal salts 116
4. Conclusions 117
8. SiO₂ Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles 121
Graphical Abstract 121
Abstract 121
1. Introduction 122
2. Materials and methods 123
2.1. Materials 123
2.2. Methods 124
2.3. Synthesis of the PMF particles 125
2.4. Water treatment experiments 128
2.5. Theoretical model 129
3. Results and Discussion 132
3.1. PMF-Std 133
3.2. Influence of the reaction mixture composition 136
3.3. Variation of the process parameters 140
3.4. Conclusion on the templating mechanism for PMF-Std 146
3.5. Acquiring µm-sized porous PMF particles for adsorption application 149
3.6. Adsorption experiments with K2Cr2O7 solution 151
4. Conclusion 155
9. Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions 161
Graphical Abstract 161
Abstract 161
1. Introduction 162
2. Materials and methods 163
2.1. Materials 163
2.2. Synthesis 164
2.3. Characterization 166
2.4. Batch adsorption experiments 169
2.5. Calculation and theoretical models 170
3. Results and discussion 172
3.1. Synthesis and characterization of the polymer particles 172
3.2. Adsorption experiments with Ni2+, Cd2+, and Pb2+ onto P(3PT-F)-3L 178
4. Conclusions 184
10. Conclusion and Outlook 191
Contribution to Publications 197
Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal 197
Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal 198
Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles 199
SiO₂ Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles 200
Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions 201
Danksagung 203
Appendix 205
References 207
Eidesstattliche Versicherung 217Durch fortschreitende Industrialisierung und den schonungslosen Verbrauch natürlicher Rohstoffe übt der Mensch negativen Einfluss auf seinen Lebensraum aus. Insbesondere Wasser als Grundlage des Lebens und fast aller Prozesse unserer Wirtschaft wird durch eine übermäßige Nutzung und unzureichende Reinigung mit diversen Schadstoffen kontaminiert. Hierbei stellen Oxyanionen, Schwermetallionen und organische Schadstoffe ein hohes Risiko für aquatische Lebensräume und letztendlich auch den Menschen dar. Durch unzureichende Entfernung tragen sie außerdem zum Verlust nicht-erneuerbarer Rohstoffe für industrielle Kreisläufe bei. Durch eine meist geringe Effektkonzentration und potentielle Wechselwirkungen mit diversen Lebewesen ist die Entfernung vieler Verunreinigungen extrem wichtig, um bestehende Ökosysteme nicht weiter zu verändern.
Adsorption stellt eine energieeffiziente Methode zur Entfernung dieser Schadstoffe durch hierfür geeignete Adsorbentien dar. Hochgradig vernetzte Harzpolymere wie Poly(melamin-co-formaldehyd) (PMF) stellen mit ihrer sehr hohen chemischen Beständigkeit, einer hohen Zahl funktioneller Gruppen und einfachen Herstellbarkeit einen vielversprechenden Ausgangspunkt für Adsorbentien dar.
Diese Dissertation beschreibt die kolloidale, wässrige Synthese nanoporöser Harzpartikel (z. B. PMF) durch eine Templatierung mit SiO2 Nanopartikeln (SiO2 NPs), welche anschließend zur Adsorption von Wasserschadstoffen eingesetzt werden. Ein übergeordnetes Ziel dieser Arbeit besteht aus der Aufklärung des Mechanismus zur Partikel- und Porenbildung durch systematische Variation verschiedener Syntheseparameter. Mittels Elektronenmikroskopie, N2-Sorption und Partikelgrößenmessung wird die Morphologie, Größe und Porenstruktur der Partikel analysiert. Umfassende Untersuchungen ermöglichen somit, den Einfluss der einzelnen getesteten Syntheseparameter auf diese Eigenschaften zu bestimmen.
Ein sehr wichtiges Ziel, besonders für eine zukünftige großtechnische Anwendbarkeit, ist dabei die kolloidale Herstellung uniformer Partikel, welche sowohl eine hohe geordnete Porosität als auch Partikeldurchmesser im Bereich einiger Mikrometer aufweisen. Dies ermöglicht einen Einsatz als durchströmbaren Festbett-Adsorber. Dieses Ziel ist eng mit der mechanistischen Aufklärung der Poren- und Partikelbildung in der Synthese verknüpft.
Die hergestellten nanoporösen PMF-Partikel wurden nach ihrer Charakterisierung für verschiedene Adsorptionsanwendungen getestet. Um ein umfassendes Bild über die Einsetzbarkeit von PMF-Partikeln zu erhalten, sollen jeweils Versuche mit Oxyanionen, mit Schwermetallionen und mit Pharmazeutika als Vertreter organischer Schadstoffe durchgeführt werden. Bei diesen Versuchen steht zum einen die Untersuchung der Adsorptionsleistung und des Adsorptionsmechanismus des jeweiligen Schadstoffes an PMF im Vordergrund. Zum anderen wird durch die Verwendung verschiedener Partikel, bei welchen ein einzelner Syntheseparameter variiert wurde, der Einfluss der veränderten Porosität auf den Adsorptionsmechanismus untersucht.
Sulfat- und Phosphationen wurden in der Klasse der Oxyanionen untersucht. Für beide Ionen wurden extrem hohe Abtrennraten nachgewiesen, welche bisherige kommerziell erhältliche Materialien signifikant übertraf. In Versuchen hinsichtlich einer potentiellen selektiven Adsorption und somit Trennung beider Spezies, zeigten die PMF/SiO2-Hybridpartikel, bei welchen das Templat noch nicht entfernt wurde, eine selektive Sulfatadsorption.
Die Immobilisierung von Schwermetallionen wurde mit besonderem Fokus auf die gleichzeitig auftretende Abtrennung der dafür verwendeten Cu2+-Ionen und jeweiliger Anionen analysiert. Durch Untersuchungen des Adsorbens nach den Adsorptionsversuchen mittels Elektronenmikroskopie, Röntgenstreuung und Elektronenspinresonanz-Spektroskopie wurde der bisher unzureichend analysierte Adsorptionsmechanismus aufgeklärt. Hierbei wurden Adsorption und oberflächeninduzierte Fällung als separate Teilprozesse identifiziert, welche beide jeweils für die Abscheidung von sowohl Metall- als auch Anionen aus der Lösung verantwortlich sind. Bei Adsorptionsversuchen mit den einwertigen Ionen Nitrat und Chlorid wurde ein zweistufiger Prozess identifiziert, welcher erstmals über eine neue Adsorptionsisotherme mathematisch beschrieben wurde.
Im Bereich organischer Wasserschadstoffe wird die Abtrennung des Pharmazeutikums Diclofenac getestet. Insbesondere die Adsorption von Pharmazeutika stellt aufgrund von deren geringen Effektkonzentration und Allgegenwärtigkeit in Oberflächen- und Leitungswässern ein dringliches Thema dar. Die Pharmazeutika-Abtrennung mittels PMF wurde trotz seiner vielversprechenden Eigenschaften weltweit bisher kaum untersucht. Im Rahmen dieser Versuche wurden Partikel getestet, welche mit unterschiedlich großen und unterschiedlich stabilisierten SiO2 NPs templatiert wurden. Dadurch entstanden Porensysteme, die besonders in derer Zugänglichkeit ihres Porensystems und in dem Durchmesser der Verbindungskanäle zwischen den Hauptkavitäten voneinander variierten. Diese Eigenschaften wirkten sich signifikant auf die Adsorptionskapazität und die Abtrennraten im niedrigen Konzentrationsbereich aus.
Ein abschließendes Ziel ist die Synthese eines Harznetzwerkes, welches statt Melamin auf einem ebenso hochfunktionellen, triazinbasierten Monomer basiert. Das Monomer 2,4,6-Tris(2,4,6-trihydroxyphenyl)-1,3,5-triazin (3PT) besitzt jeweils neun Hydroxylgruppen, wodurch ein darauf basierendes Polymer stark veränderte Adsorptionseigenschaften gegenüber PMF aufweisen soll. Mit diesem Monomer wurde in einer analog zu PMF durchgeführten wässrigen Polymerisation ein bisher unbekanntes Polymernetzwerk hergestellt, welches als P(3PT-F) bezeichnet wurde. Hierbei wurde auf Templatierung verzichtet, da das neu hergestellte Material bereits intrinsische Nanoporosität durch die Größe des verwendeten 3PT-Monomers aufwies. In anschließenden Adsorptionsversuchen wurden sehr hohe Abtrennraten für die toxischen Metallion Pb2+, Cd2+ und Ni2+ nachgewiesen. In realistischen Ausgangskonzentrationen wurde die Kontamination mit diesen Ionen jeweils auf Trinkwasserqualität reduziert. P(3PT-F) zeigte außerdem eine sehr selektive Abtrennung von Pb2+ gegenüber den häufig vorkommenden Ionen Ca2+, Mg2+, K+ und Fe2+. Als grundlegender Beweis konnte eine Wiederverwendbarkeit durch die vollständige Desorption mit verdünnter HCl gezeigt werden und eine anschließende erneute Adsorption ohne signifikante Verringerung der Kapazität.
Insgesamt wurde ausgehend von der grundlegenden Untersuchung der PMF-Partikelsynthese erst ein generelleres Verständnis der wässrigen Dispersionspolymerisation hydrophober Harze abgeleitet und die Templatierung mit hydrophilen SiO2 NPs implementiert. Mithilfe des Verständnisses der Partikelwachstumsprozesse und der Wechselwirkungen, welche für die Templatierung verantwortlich sind, konnten die Eigenschaften der entstehenden Partikel gesteuert werden. Im Rahmen der Adsorptionsuntersuchungen konnte anschließend der Einfluss insbesondere der veränderten Porosität auf die Abtrennleistung untersucht werden. Außerdem konnte analysiert werden, welche Wechselwirkungen PMF mit den jeweiligen Schadstoffarten eingeht. Durch den Austausch des Monomers Melamin gegen das hydroxylhaltiges Monomer 3PT konnte ein neuartiges Harzpolymer hergestellt werden. Dieses kann mit seiner veränderten Porosität und Reaktivität nun als neuer Ausgangspunkt für Adsorptionsexperimente mit stark veränderter Adsorptionsleistung z. B. gegenüber Schwermetallionen dienen.:Abstract 1
Kurzfassung 5
List of Publications 9
First-Author Publications 9
Co-Author Publications 10
Patent 12
Conference Proceedings 12
Oral Presentations 12
Poster 12
List of Figures 13
Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 14
Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 15
Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 16
SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 18
Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 19
List of Tables 21
Mesoporous Poly(Melamine-co-Formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal: 21
Tuning the Pore Structure of Templated Mesoporous Poly(melamine-co-formaldehyde) Particles toward Diclofenac Removal: 21
Adsorption vs. Surface Precipitation of Cu²+ onto Porous Poly(melamine-co-formaldehyde) Particles: 22
SiO2 Nanospheres as Surfactant and Template in Aqueous Dispersion Polymerizations Yielding Nanoporous Resin Particles: 22
Waterborne Phenolic, Triazine-Based Porous Polymer Particles for the Removal of Nickel, Cadmium, and Lead Ions: 23
Abbreviations 25
Symbols 26
1. Introduction 1
2. Objectives and Experimental Design 5
3. Scientific Background 11
3.1. Poly(melamine-co-formaldehyde) 11
3.1.1. Polymerization Mechanism 11
3.1.2. Synthesis Strategies for the Preparation of Porous PMF Particles. 13
3.1.3. Fields of Application of PMF 13
3.2. Adsorption 15
3.2.1. Adsorption Isotherms and Mathematical Modeling 16
3.3. Surface Precipitation 20
4. Fundamentals of Instrumental Analytics 23
4.1. Gas Sorption Measurements 23
4.1.1. Determination of
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