Doctoral Thesis

Use of cement hydration accelerators to suppress the negative effects of zinc compounds on the properties of Portland cement

Final Thesis 1005.48 kB Appendix 15.55 MB

Author of thesis: Ing. Lukáš Matějka

Acad. year: 2025/2026

Supervisor: doc. Ing. František Šoukal, Ph.D.

Reviewers: Assoc. Prof. Anatolijus Eisinas, PhD., prof. Dr. Ing. Martin Palou

Abstract:

The doctoral thesis focuses on the rising concentration of zinc in ordinary Portland cement (OPC) that impacts the behaviour of cement-based mortars by drastically prolonging setting time and decreasing early mechanical properties. The current theory behind the mechanism of the effect of this contaminant is the depletion of Ca2+ ions from pore solution and the formation of a semipermeable layer of CaZn2(OH)6∙2 H2O on the surface of silicate cement phases, thus retarding their hydration.
    One of the main solutions to retarded setting of cement-based binders in the industry is the addition of setting accelerators. These additives, commonly composed of chlorides, nitrates, thiocyanates and organic compounds, are widely used to counteract the low reactivity of SCMs, low temperatures and retarded setting in waste immobilisation. They differ in mechanism of action, effectiveness and application. The efficiency of these additives to compensate for the negative effects of zinc compounds on the properties of cement is not very well researched.
    The results presented in this work demonstrated varying effectiveness of both pure compounds and commercial accelerators at accelerating the hydration of zinc-contaminated OPC. Thiocyanates, which are commonly contained in commercial additives, caused further retardation of setting through destabilisation of ettringite by high alkali content and increased ionic strength of pore solution. This also resulted in a decrease in compressive strength. Pure nitrates outperformed commercial counterparts. They reduced the setting time of ZnO-OPC from around 180 hours to around 50 hours. The commercial nitrate-based additives reduced the setting time to only around 100 hours. Higher acceleration of setting also resulted in a visible improvement in mechanical properties.
    The effectiveness of setting the accelerator is heavily connected to the content of ettringite in the sample. All ineffective or detrimental additives had compromised the formation of ettringite in the samples. The best results were achieved by using formate salts. Calcium formate in higher doses reduced the setting time to a comparable timeframe of pure OPC, with visible improvement of compressive strength after 28 days of curing. This compound promotes the formation of ettringite, thus improving setting time and mechanical properties of the ZnO-OPC system.

Keywords:

Keywords: Portland cement, Zinc oxide, Hydration retardation, Setting accelerators, Thermal analysis, XRD, formate salts

Date of defence

22.06.2026

Result of the defence

Defended (thesis was successfully defended)

znamkaPznamka

Process of defence

Předseda komise představil doktoranda a předal mu slovo. Obhajoba probíhala v angličtině. Ing. Matějka má určité pracovní zkušenosti - PROJEKCE IGEO, s.r.o., na dvou různých pozicích od června 2022 do května 2025. V akademickém roce 2021/2022 absolvoval půlroční zahraniční stáž na Clausthal University of Technology. Zúčastnil se celé řady konferencí v České republice a v zahraničí. Podílel se na několika projektech. Je spoluautorem několika publikací v impaktovaných časopisech. The committee chair introduced the doctoral student and gave him the floor. The defense was conducted in English. Ing. Matějka has some work experience – PROJEKCE IGEO, s.r.o., in two different positions from June 2022 to May 2025. In the academic year 2021/2022 he completed a six-month internship at Clausthal University of Technology. He attended a number of conferences in the Czech Republic and abroad. He was involved in several projects. He is a co-author of several publications in impact journals.

Language of thesis

English

Faculty

Department

Study programme

Chemistry, Technology and Properties of Materials (DPCP_CHM_4_N)

Composition of Committee

doc. Ing. Lukáš Kalina, Ph.D. (předseda)
prof. Ing. Jiří Zach, Ph.D. (člen)
prof. Ing. Bedřich Smetana, Ph.D. (člen)
prof. Dr. Ing. Martin Palou (člen)
prof. Ing. Vlastimil Matějka, Ph.D. (člen)
Assoc. Prof. Tadas Dambrauskas, PhD. (člen)
Assoc. Prof. Anatolijus Eisinas, PhD. (člen)

The doctoral thesis submitted by Ing. Lukáš Matějka addresses a highly relevant and scientifically significant topic concerning the influence of zinc compounds on the hydration of Portland cement and the possibility of mitigating these adverse effects through the use of hydration accelerators. The subject is closely connected with current trends in the cement industry, particularly the increasing use of alternative fuels and secondary raw materials, which contribute to elevated concentrations of trace elements in cement raw materials and binders. The topic is also important in the field of hazardous waste immobilisation using cementitious materials. 
The dissertation summarizes the results of long-term research conducted within a grant-funded project focused on suppressing the negative effects of zinc contamination in Portland cement. During his doctoral studies, the candidate actively participated in the design of experiments, preparation of samples, execution of measurements, evaluation of results, and their interpretation. He gradually acquired extensive expertise in a broad range of experimental techniques commonly used in the study of cement hydration, including isothermal and isoperibolic calorimetry, thermal analysis, and X-ray diffraction. 
The thesis is logically structured and well organized. The literature review provides a comprehensive overview of the current state of knowledge regarding Portland cement hydration, the effects of zinc on hydration processes, and the application of various hydration accelerators. This section is followed by the presentation and discussion of the candidate's original research results, which are based on published scientific papers.
Among the most important achievements of the dissertation are:
•    a systematic clarification of the differences between the effects of soluble zinc compounds and zinc oxide on the hydration of Portland cement,
•    demonstration of the synergistic effect of zinc and ground granulated blast-furnace slag leading to significant prolongation of setting time,
•    clarification of the role of ettringite formation in mitigating the negative effects of zinc on cement hydration,
•    experimental verification of the effectiveness of several groups of hydration accelerators,
•    demonstration of the unsuitability of alkaline thiocyanates for ZnO-contaminated cement systems,
•    evaluation of the performance of both commercial and pure nitrate-based accelerators,
•    identification of formate salts, particularly calcium formate, as highly effective accelerators capable of substantially reducing the setting time of ZnO-containing Portland cement while maintaining or even improving the mechanical properties of the hardened material. 
The results presented in the thesis are not only scientifically valuable but also possess considerable practical potential for application in the cement industry. They contribute to a better understanding of the mechanisms responsible for zinc-induced retardation of cement hydration and provide practical recommendations for the design of cementitious systems containing elevated levels of heavy metals.
The quality of the candidate's work is further demonstrated by his publication record. He is a co-author of several scientific papers published in international journals indexed in the Web of Science and Scopus databases, and he is the first author of a number of these publications. He has also presented the results of his research at national and international scientific conferences.   
Throughout his doctoral studies, Ing. Lukáš Matějka demonstrated the ability to conduct independent scientific research, critically evaluate experimental results, and communicate scientific findings effectively. He actively participated in research projects and made a significant contribution to the research activities of the department. I particularly appreciate his systematic approach, diligence, attention to detail in experimental work, and ability to solve complex research problems.
From both scientific and formal perspectives, the dissertation fulfils the requirements expected of a doctoral thesis. It presents original scientific findings and clearly demonstrates the candidate's ability to independently conduct advanced research and solve demanding scientific problems.

Conclusion
I state that Ing. Lukáš Matějka has successfully fulfilled the objectives of his doctoral studies as well as the goals defined in the dissertation thesis. I therefore recommend the dissertation for defence and, upon its successful defence, I recommend that Ing. Lukáš Matějka be awarded the academic degree of Doctor of Philosophy (Ph.D.).
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Posudek oponenta [.pdf] 110,17 kB

Reviewer’s report
prof. Dr. Ing. Martin Palou

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Posudek oponenta [.pdf] 212,46 kB

Responsibility: Mgr. et Mgr. Hana Odstrčilová